Real and Liverpool will be confident of progressing from Group B where debutants Ludogorets of Bulgaria, who were only formed in 2001 and whose stadium holds just 8,000 fans, and Swiss outfit Basel, who knocked out Manchester United at this stage three years ago, await.
Liverpool boss Brendan Rodgers told his club's website: "Hopefully it was great for the supporters to sit and watch the draw for the first time in five years.
"To be back in it again, no matter who we were going to play, it was always going to be exciting. But to have Real Madrid in your group, the champions last season, is going to be special.
"I'm already thinking of Anfield on that night."
Real are relishing the trip to Merseyside.
"Liverpool are an historic club of this great competition," Real director Emilio Butragueno said.
"They are a great club and they have a stadium which is one of the cathedrals of football, therefore at Anfield they are especially strong.
"The support of their fans is extraordinary and they will be a very dangerous opponent."
Butragueno added: "It is an additional challenge for our players to be able to break this tradition of the holders not being able to retain the trophy."
Group F sees four-time winners Barcelona come up against PSG, who recruited Brazilian centre-back David Luiz from Chelsea in the close season.
He will be meeting a familiar foe in new Barca signing Luis Suarez, the former Liverpool forward.
Four-time former winners Ajax, another of Suarez's previous sides, are alongside the pair as well as Cypriots Apoel.
Another money draw saw 2013 champions Bayern Munich paired with Manchester City, Roma and CSKA Moscow in Group E.
It is the third time in four years that Bayern and City will have faced each other in the group stages.
For English Premier League winners City, who failed to progress from the group stages in two of the last three years, it continues a run of tough draws at this stage of Europe's premier club competition.
In 2011/12 they were paired with Bayern and Napoli and missed out on the knock-out stages after failing to beat the Italians at home.
A year later they finished bottom of a group containing Real, Borussia Dortmund and Ajax as they failed to win a single game.
Only last year, when they were also thrown in with Bayern, did City manage to get through the group stages and this time their job will not be simple.
There was a kinder draw, on paper at least, for 2012 champions Chelsea, who poached Germans Schalke 04, Sporting Lisbon of Portugal and Slovenia's Maribor in Group G.
Arsenal, bidding to reach the knock-out stages for the 12th year in a row, plucked Borussia Dortmund, the 2013 finalists, in a tough Group D with Galatasaray, who beat them in the 2000 UEFA Cup final, and Belgian giants Anderlecht.
Arsenal captain Mikel Arteta tweeted: "Dortmund again and two new and tough teams. I love playing Champions League. Come on Gunners."
Last year's runners-up Atletico Madrid, the Spanish champions, pulled Italian champions Juventus out of the hat in Group A, along with Greeks Olympiakos, who regularly struggle at this stage, and Swedes Malmo, the European Cup runners-up from 1979.
Portuguese pair Porto and Benfica were given manageable draws, the latter getting Ukrainians Shakhtar Donetsk, Athletic Bilbao of Spain and Belarus representatives BATE Borisov in Group H.
Benfica, the twice former winners, were drawn against Russians Zenit St Petersburg, coached by former Porto boss Andre Villas-Boas, Bayer Leverkusen of Germany and Russian-backed Monaco in Group C.
The fairytale appearance meanwhile of Bulgarian minnows Ludogorets in Group B is due in large part thanks to the heroics of defender Cosmin Moti.
He was forced into goal in the last minute of extra-time of their play-off second leg 1-1 draw with Romanians Steaua Bucharest after goalkeeper Vladislav Stoyanov was dismissed in the final minute.
The game went almost immediately into penalties where not only did Moti score his side's first spot-kick but he saved two of the Romanians' to send the Bulgarians into the lucrative group stages.