New faces but few surprises expected
Champions Barcelona, their big-spending Spanish rivals Real Madrid and England's quartet of Manchester United, Chelsea, Liverpool and Arsenal are all odds-on with the bookmakers to win their groups outright.
The remaining big guns from Spain along with the top teams in Italy and Germany are also tipped to qualify for the last 16, leaving lesser-known teams to battle for third spot and the consolation of a place in the second-tier Europa League.
Barcelona are the bookmakers' favourites to become the first club to win back-to-back Champions League titles since the elite competition was reformed in 1992 and their credentials will immediately be put to the test on Wednesday when they travel to Inter Milan for their opening Group F encounter.
Inter have been the perennial under-achievers in Europe but hope the arrival of striker Samuel Eto'o from Barcelona and the exit of unsettled and inconsistent Zlatan Ibrahimovic in the opposite direction will pay dividends.
On paper, last season's runners-up Manchester United should win Group B, but manager Alex Ferguson believes the Premier League champions face the toughest challenge of all England's four contenders.
United make the long trip to Turkey on Tuesday to face Besiktas before entertaining German champions Vfl Wolfsburg at Old Trafford.
Another long trip to Russia to play CSKA Moscow sandwiched in between a busy domestic schedule and having to navigate the artificial surface at Moscow's Luzhniki Stadium have left Ferguson with concerns.
"We were talking about it beforehand and saying we didn't want to go to Russia because of the length of the journey - and Turkey is the same. Then we get the two of them," Ferguson said after last month's draw. There are no such travel concerns for Real Madrid, but expectations are high of reaching the final at their Bernabeu home in May after president Florentino Perez spent 250 million euros on new talent, including Kaka, Cristiano Ronaldo, Karim Benzema and Xabi Alonso.
Madrid are away to FC Zurich in their opening Group C match on Tuesday before home ties against Olympique Marseille and AC Milan. Kaka's move from Milan to Madrid gives the two fixtures between the sides an extra edge.
Chelsea - semi-finalists in five of the last six years - hope coach Carlo Ancelotti can continue his Champions League success. The Italian has won the competition twice as a player and twice as a coach - all with AC Milan.
"I don't know if I am an expert on the Champions League but ... I think it is the most important competition in the world and a very difficult one to win," Ancelotti said.
The Londoners kick off at home to Porto on Tuesday before facing Cypriots APOEL Nicosia and Atletico Madrid in Group D.
Liverpool face a couple of tricky encounters in Group E where Fiorentina and Olympique Lyon await but they start with an easier task on Wednesday at home to Hungary's Debrecen.
Arsenal should be confident of winning Group H and getting off to a winning start at Standard Liege on Wednesday before facing Olympiakos Piraeus of Greece and Dutch side AZ Alkmaar.
Spain's Sevilla will look to finish top of Group G where Rangers, VfB Stuttgart and Romania's Unirea Urziceni are all capable of grabbing the second qualifying place.
Top spot in Group A looks a straight fight between Bayern Munich - buoyed by the arrival of Arjen Robben and retention of Franck Ribery - and Juventus who won their opening three Serie A games thanks mainly to their inspirational new signing Diego.
But Girondins Bordeaux and Israel's Maccabi Haifa are capable of winning some games and causing an upset.