Following a string of disappointments last season and with three new managers at the helm, all four of England's representatives will be looking for a marked improvement
Manchester City and Chelsea failed to get out of the group stage last time around, while Arsenal and Manchester United were dumped out of the competition at the first knockout stage.
All four were left to watch from the sidelines as the top clubs from Germany and Spain, in particular, lit up the latter stages with a series of breathtaking ties, including Bayern Munich's 7-0 aggregate victory over Barcelona and Borussia Dortmund's stunning comeback against Malaga and home demolition of Real Madrid.
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It has been four years since Arsene Wenger negotiated his side past the first knockout stage and he will be under pressure to make strides this season following the club-record £40 million purchase of Mesut Ozil from Real Madrid.
Wenger has put his faith in the Germany international, who laid on 16 goals in 31 Champions League appearances for Los Blancos, to take his side next level at home and abroad, but this competition has a habit of exposing a team's weaknesses.
And there will be little room for error in arguably the toughest group of the lot. With Napoli, Marseille and last season's beaten finalists Dortmund also vying for qualification from Group F, Wenger's squad will be pushed to its limits.
The old adage that 'there are no easy games at this level' is certainly true for Manchester United's campaign, too. It may be nigh-on impossible for David Moyes to better Sir Alex Ferguson's 27-year Old Trafford reign but he can certainly improve on their recent performances in Europe.
Having sealed qualification to last season's knockout stage, United lost to Galatasaray and Cluj in their final group fixtures before being knocked out by Real Madrid. Of course, they did not even get as far as the knockouts in 2011-12.
Moyes will have his first crack at the competition proper and will be hoping that the youngsters in United's squad, such as David de Gea, Rafael, Phil Jones, Chris Smalling, Tom Cleverley and Danny Welbeck, will have learned from some of their harsh lessons in recent years.
But, like Arsenal, United will not have it easy. Shakhtar Donetsk, Bayer Leverkusen and Real Sociedad lie in wait, meaning that there will be few opportunities to rest players even for the 'easier' home fixtures, as has been possible over the years. Though maybe that could be a blessing in disguise.
Manchester City's travails in the competition are well documented. After Roberto Mancini presided over two group-stage eliminations, the club's hierarcy decided that it was time for a change. Manuel Pellegrini, with his vast European experience, is the man chosen to take the City project to the next level.
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It is clear everybody is on the same page at the Etihad Stadium and this year they will expect a vast improvement. Viktoria Plzen, CKSA Moscow and Bayern Munich stand in City's way as they look to build a European portfolio befitting the millions of pounds they have spent since 2008.
City finished bottom of their, albeit difficult, group last season but, if their elimination was embarrassing, Chelsea's was downright ignominious. The Blues became the first defending champions of the modern competition's 20-year history to fail to get out of the group, meaning Roberto Di Matteo was relieved of his duties just months after delivering the famous trophy.
Of course, Jose Mourinho is back in town and he will be extremely confident (even more so) of going far in the tournament. Schalke, Basel and Steaua Bucharest are no mugs but Mourinho has overcome tougher opponents in his time. Indeed, the Portuguese has reached at least the semi-finals in his last three Champions League seasons, including winning the lot with Inter in 2010.
Britain's other proud representatives, Celtic, will certainly have a fight on their hands. If they are to repeat last season's feat of emerging from the group, they will have to surpass two of Barcelona, AC Milan and Ajax. Famously, the Bhoys downed Barca at Parkhead last season and the Rossoneri at the same venue in 2007, so don't rule out the improbable.
Elsewhere, two of Europe's giants go head-to-head in Group B, with Real Madrid and Juventus joined by Galatasaray and Copenhagen. Madrid's city rivals, Atletico, must contend with an equally tough set of fixtures against Porto, Zenit St Petersburg and Austria Vienna.
Paris Saint-Germain, who came so close to knocking out Barcelona last season, will go again alongside Benfica, Anderlecht and Olympaikos.