Holders Real Madrid are 9.0 in bwin’s Champions League winner odds after receiving a favourable group-stage draw in Istanbul.
The 14-time victors are in Group F alongside RB Leipzig, Shakhtar Donetsk and Celtic, who can be backed at 251.0.
Manchester City are 3.75 favourites to lift the trophy for the first time after coming out in Group G with Sevilla, Borussia Dortmund and FC Copenhagen.
For City, last season’s beaten semi-finalists, big summer signing Erling Haaland will get a speedy reunion with former club Dortmund.
CEO Ferran Soriano commented: “I guess you can never be completely happy with the draw but I think we have good teams to play.
“Dortmund will be a special game for Erling Haaland and also Ilkay Gundogan. I think both will enjoy it, it is a fantastic stadium.
“Last time we went there, it was empty because of Covid, so it will be a great experience for fans of each team and we’re very excited.”
Asked about the significance of ending their Champions League hoodoo, Soriano added: “Our priority is always the Premier League. We work for it every day. It is our bread and butter.
“The Champions League is of course an aspiration but it’s not an obsession. We will win it one day, I am sure.”
Reds facing Battle of Britain
Liverpool can be backed at 251.0 outsiders Rangers.
Former Anfield star Steve McManaman told BT Sport: “I think Liverpool’s draw is possibly the most difficult out of the English teams.
“Ajax and Napoli are tough places to go and the ‘Battle of Britain’ games with Rangers will be brilliant.”
Chelsea will be content with drawing AC Milan, RB Salzburg and Dinamo Zagreb in Group E and are 17.0 to add to their 2012 and 2021 triumphs.
Tottenham complete the quartet of Premier League sides involved and they are 15.0 after coming out with Eintracht Frankfurt, Sporting Lisbon and Marseille in Group D.
Group C looks to be the toughest section, with Bayern Munich quoted at 51.0, while Viktoria Plzen have a mountain to climb to advance.
PSG are 29.0 Juventus in Group H, with Benfica and Maccabi Haifa the outsiders to progress there.
Group B contains Porto, Atletico Madrid, Bayer Leverkusen and Club Brugge, with the Spanish outfit fancied to fare best at 41.0.
The opening round of matches will be played on September 6 and 7, while the final is at Ataturk Olympic Stadium in Istanbul on June 10.
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