The reigning champion discovered who it will face in the group stages on Thursday, with other top ties including Arsenal-Dortmund, Bayern-Man City and Atletico Madrid-Juventus.
Reigning European champion Real Madrid has been drawn with five-time winner Liverpool in the Champions League group stage draw held in Monaco on Thursday.
Carlo Ancelotti's men achieved la Decima in May with a final win over Atletico Madrid and they will also face Swiss side Basel and Bulgarian champion Ludogorets in Group B as Madrid tries to become to first team in Champions League history to win back-to-back titles.
Bayern Munich, coached by former winner Pep Guardiola, will aim for a fourth final in six years but has arguably been handed the Group of Death as the club will need to overcome Premier League winner Manchester City, Russian side CSKA Moscow and Serie A runner-up Roma to get out of Group E.
Barcelona will need to navigate a way past Paris Saint-Germain - led by former striker Zlatan Ibrahimovic - Dutch champion Ajax and Cyprus minnow APOEL.
Chelsea, Champions League victor in 2011-12, was given a relatively straightforward draw as the English club faces out-of-sorts Schalke, Portuguese opposition Sporting and Slovenian side Maribor.
Arsenal is still without a Champions League title to its name and will have a bumpy ride just reaching the last 16 as 2012-13 finalist Borussia Dortmund, Galatasaray and Belgian champion Anderlecht provide competition.
Atletico Madrid, runner up last season after taking Real Madrid to extra time, will be confident it can share one of the top two spots with Scudetto holder Juventus, Olympiakos and outsider Malmo.
Last season's Europa League runner up Benfica, Bundesliga big hitter Bayer Leverkusen, Andre Villas-Boas' Zenit St-Petersburg and Ligue 1 runner up Monaco make Group C one of the most competitive sections.
Contrastingly, Porto will be confident of making amends for failing to reach the knockout stages in 2013-14 after being drawn alongside Shakhtar Donetsk, Athletic Bilbao and BATE.
Each of the top two teams will qualify for the last 16 draw in December. The 2013-14 final, the 60th organized by UEFA, will be held at the Olympiastadion in Berlin on June 6.