Their five-year absence from Europe's premier competition left them with the task of negotiating a group that contains Real Madrid, FC Basel and Ludgorets, and in truth, it could have been a lot worse for the five-time winners.
The pairing with 10-time winners and current holders Real Madrid will give everyone connected with the club a huge lift, and fans will be eagerly anticipating the visit from Los Blancos, who they last met back in the 2008-2009 season, when they hammered the Spaniards 5-0 on aggregate.
The Reds were a breath of fresh air in the Premier League last season and eventually finished second in the Premier League, two points behind champions Manchester City, and Brendan Rodgers' side scored 101 goals en route to a runners-up finish.
However, their lack of European participation certainly helped the side in their domestic hunt and Hamann thinks that it will be a lot different now they are back in the big time.
The German, who won the 2005 Champions League with the Reds, thinks that their relative lack of experience on the European stage will hinder them and thinks that they will struggle.
He told Sky Sports News: "Liverpool have a tough year ahead of them, they will have to get used to playing on a Wednesday and then a Saturday and a lot of their players haven’t been there before.
"With that being said, I think Liverpool will have it tough this season. I think it suits them better in the Champions League than the Premier League.
"They have a lot of players who haven’t played there before, but they’ve all got potential., they’re young players with great potential but it’ll be tough."
Liverpool have spent close to £120 million with summer on Emre Can, Dejan Lovren, Adam Lallana, Rickie Lambert, Lazar Markovic, Javi Manquillo, Alberto Moreno, Mario Balotelli and Divock Origi, who will join the Anfield side after his season-long loan spell with Lille is over.