The Blues will have to be at their best to beat Italian champions Juventus who were the Pot 3 team that everyone wanted to avoid, with Roberto Di Matteo hoping to win the competition for the second successive season.
In Group F, we have two European heavyweights competing at the Allianz Arena, with Bayern facing Valencia, while tournament favourites Barcelona open their campaign with an easy-looking match against Spartak Moscow.
Celtic kick things off with a tricky opener against Benfica, while Manchester United will start their European adventure with a home match against Galatasaray.
Chelsea v Juventus 19:45
What to make of Chelsea this season? Roberto Di Matteo’s season won successive matches against Wigan, Reading and Newcastle although they were soundly beaten by Manchester City in the Community Shield and humbled by Atletico Madrid in the Super Cup which suggests retaining their Champions League crown is a big old ask this season.
The Blues will be looking to make a fast start against the Italian champions with both teams likely to emerge from Group E and Chelsea are 5/4 (BetVictor) to claim three points from this contest at Stamford Bridge.
Eden Hazard has enjoyed a fine start since completing his big money move from Lille and there is little doubt that the Belgian will rise to the big occasion here, with odds of 9/1 (Coral free bets) available that he opens the scoring.
However, Hazard might be more of an assist-provider against the Turin side, with Frank Lampard a 9/1 chance to score first and he is likely to be on penalty duties against a Juve side that have enjoyed a strong start to their domestic season.
Juventus have won all three Serie A fixtures scoring nine goals in the process and they will be going for the win in this match, with odds of 12/5 (Paddy Power) on offer that the visitors are celebrating come the final whistle.
Many players in the Italian team that reached the Euro 2012 final are part of this Juventus side and this includes Andrea Pirlo who remains a sensational ball passer who provides plenty of ammunition for forwards such as Mirko Vucinic.
Manchester United v Galatasaray 19:45
Sir Alex Ferguson has vowed to take the Champions League deadly seriously this season after his decision to rest players in fixtures last term saw Benfica and Basel qualify at the Red Devils’ expense.
The signing of Robin van Persie has been made for a number of reasons and one of them is the hope that the Dutchman will provide the killer instinct in Europe, with the striker looking to make hay against Gala on Wednesday night.
Many midweek accumulators will include United at odds of 1/3 (Paddy Power) and the English side do appear to be moving through the gears, having beaten Wigan Athletic 4-0 on Saturday afternoon.
Ferguson will want a comprehensive victory to kick things off ahead of matches against Braga and Cluj, with Van Persie a 3/1 chance to score first and some might like the 14/1 about the forward bagging a hat-trick, having been left on the bench for the last match.
Galatasaray won the Turkish Super Lig last season and previous Gala teams have caused problems for United at Old Trafford although it’s a big ask for the visitors in this match, even if they are coached by the experienced Fatih Terim.
Even so, the Red Devils have not convinced in defence and the Turkish side are 11/1 to claim three points and cause Ferguson to scratch his head as to how the problems at the back can be solved.
Celtic v Benfica 19:45
Celtic have done well to fend off HJK Helsinki and Helsingborgs to ensure they are lining up in the Champions League group stage although Neil Lennon’s side could be out of their depth at this stage of the competition.
The Hoops’ domestic form suggests that Wednesday’s match against Benfica could be a struggle ahead of them facing Barcelona and Spartak Moscow, with Lennon disgusted after watching his team lose 2-1 at St Johnstone following that 2-2 draw at home to Hibernian.
Perhaps the Celtic players are distracted by the prospect of a return to the Champions League and we can be sure that Parkhead will be packed to the rafters for this contest, with odds of 3/1 (Stan James) available that the Portuguese side are beaten.
Jorge Jesus’ team will be expecting to make the knockout stage with Barcelona and they will be heavily backed 11/10 to return south with a maximum haul, with Oscar Cardozo remaining a potent threat for the visitors.