It had all looked so dangerous before the game, with victory needed to absolutely guarantee qualification, but nerves were quickly settled when after two minutes Drogba had put us in front when he danced around a defender inside the box and smashed low into the bottom corner.
The same player turned creator for the second when he sent Ramires through, though the goal owed as much to the midfielder's persistence in chasing a speculative through ball as it did the slide-rule pass in behind the defence.
It was not all plain sailing though, as in between Valencia struck a post and Petr Cech pulled off a save of world-class proportions to deny David Albelda an equaliser, but Chelsea rarely looked threatened afterwards.
Drogba rolled in a third 15 minutes from time to make three huge points safe, and the Stamford Bridge party could begin.
Genk's draw at home to Bayer Leverkusen only served to improve the mood, as we sneak through top of the group into next Friday's draw for the last 16.
A minute after netting the third, Drogba was withdrawn to huge applause around the Bridge having turned in one of his best displays in memory, a performance quickly acknowledged to the 33-year-old by every member of Chelsea's backroom team and substitutes.
There was one change from the side that started at Newcastle on Saturday, Frank Lampard replaced in midfield by Raul Meireles which meant Drogba kept his place in attack having scored the first of our three at the weekend.
Oriol Romeu continued at the base of the midfield for his fourth consecutive start having impressed over the past 10 days, so that meant John Mikel Obi joined Lampard and Fernando Torres among the subs.
Only Michael Essien and Josh McEachran were unavailable for selection ahead of this one, though Andre Villas-Boas had stated at the weekend that while the futures of Alex and Nicolas Anelka were in doubt, they would not be taking part in first-team activity.
Andre Villas-Boas and his men knew a win would guarantee a place in the last 16, but anything else would throw qualification into serious doubt.
A goalless draw would suffice provided Genk did not beat Bayer Leverkusen in the group's other game tonight, but a score draw would see Chelsea eliminated on goals scored to the benefit of our Spanish opposition.
If ever there was cause for nerves, this was it, yet it was the visitors who succumbed to the pressure. Inside three minutes Valencia had given the ball away needlessly four times, and after Meireles had tested Diego Alves with a bending effort, we went in front through Drogba.
Daniel Sturridge nicked the ball inside the Valencia half and crossed deep to former Valencia man Mata, who brought the ball down and pulled it back for the forward to control and fire home with his left foot into the far corner.
Valencia were quickly on the lookout for an equaliser though, and before five minutes were up they had struck the woodwork when attacking left-back Jordi Alba had broken into the Chelsea box and cracked an effort against Petr Cech's near post with the goalkeeper beaten.
Minutes later David Albelda, the captain, had produced a stunning drive from range destined for the top corner until Cech extended every inch of his 6ft 5ins frame to tip it behind for a corner.
There had not yet been time to pause for breath and this was perhaps just as well, because when respite did come the vulnerability of Chelsea's position came immediately to mind. One Valencia goal would still knock us out.
There was enough experience in this Chelsea side to stand strong though, Cech had done his bit, John Terry was clearing everything inside the box, and then Drogba created a second, killer goal.
The Ivorian showed pace and power to run at the away defence before adding a little guile too, slipping a ball through for Ramires in behind the defence, and while defender Victor Ruiz was favourite, the Brazilian had determination to succeed, got round his man and slotted it calmly beyond Diego Alves. This had been the perfect start, with 21 minutes on the clock.
Sturridge had a right-footed drive pushed around the post and Meireles flashed one wide while at the other end Tino Costa drove two yards off target with Chelsea looking comfortable despite Valencia enjoying the majority of possession.
The Blues went in at the break looking in complete control, though Villas-Boas will have warned that one slip would allow Valencia straight back into contention.
A low-key start to the second half came to life when Romeu set Sturridge away on a counter-attack after winning the ball on the edge of his own box, and having skinned his marker, Sturridge forced Diego Alves into a decent stop at his near post.
Cech was called into action when Sofiane Feghouli broke into the box but the keeper was on fine form and able to palm the shot away, before defensive reinforcement arrived in the form of John Mikel Obi who replaced Ramires in midfield. He would sit deep alongside Romeu, allowing Meireles to go foraging further forward in what effectively became a 4-2-3-1.
Valencia still searched but it was Drogba who should have netted to kill the contest. Sturridge produced some classy footwork and sent the forward away in a tussle with a defender, and having beaten his man should have hit the net but, under pressure, dragged wide across goal.
Even at that stage, with a little under 20 minutes still to play, it did not look like mattering too much. Then, when Drogba went through once more, he made it absolutely sure that his previous miss could be forgiven, rolling the ball calmly beyond Diego Alves after Mata had been gifted the ball in dangerous territory.
Moments later Drogba departed the field, with Torres on in his place, to rapturous applause from an adoring Stamford Bridge.
Cech had to palm away an Aritz Aduriz header and clutch onto a Pablo Hernandez drive as the minutes ticked away, but the win was never in doubt and the Blues go marching into the knockout rounds.
Chelsea (4-3-3): Cech; Ivanovic, David Luiz, Terry (c), Cole; Ramires (Mikel 64), Romeu, Meireles; Sturridge, Drogba (Torres 77), Mata (Malouda 82).
Unused subs Turnbull, Ferreira, Lampard, Kalou.
Goals Drogba 2, 75 Ramires 21
Booked Romeu 67
Valencia (4-2-3-1): Diego Alves; Barragan, Rami, Victor Ruiz, Jordi Alba (Aduriz 54); T Costa (Parejo 75), Albelda (c); Feghouli (Pablo Hernandez 64), Jonas, Mathieu; Soldado.
Unused subs Guaita, Mehmet Topal, Piatti, Dealbert.
Booked Tino Costa 68
Referee Gianluca Rocchi (Italy)