Midfielder Frank Lampard and Dutch striker Jimmy Floyd Hasselbaink put Chelsea 2-0 up at the break before Irish playmaker Damien Duff tapped in the third and Argentine forward Hernan Crespo came on to score twice.
The totally one-sided game left Chelsea on 13 points, ahead of Arsenal on goal difference and a point clear of champions Manchester United. Their two pursuers meet in Sunday's showcase game at the Old Trafford, Manchester.
Title contenders ever since Russian billionaire Roman Abramovich bought the club in July and spent £111 million ($180.5 million) rebuilding the team, Chelsea could easily have been 5-0 up at half-time, but for some missed chances and a disallowed goal.
Chelsea coach Claudio Ranieri told Sky Sports later: "I was curious to see my players after their first Champions League game and they played very, very well. Everybody was focused on the match."
Duff and Crespo, who cost some £17
The coach rubbished media reports linking England coach Sven-Goran Eriksson with the manager's job at Chelsea.
Wolves boss Dave Jones, whose promoted side are rock-bottom with one point and only one goal scored, was very disappointed with his players for giving Chelsea so much space.
"They [Chelsea] are good players, but you've got to match that and compete with that," Jones said. "Players have got to stand up and be counted.
"There is a lot of anger [in the dressing room]. It hurts us, it hurts me, we're not used to losing games like this -- I want some fight from them."
Fourth-placed Manchester City play Fulham later today needing a 4-0 win to knock Chelsea off the top of the table.