Liverpool must overcome a tricky trip to Toulouse if they are to reach the Champions League group stage.
The Reds, who have won the competition five times and were beaten in last season's final, must face the Ligue 1 side over two legs for a place in the lucrative section of the competition.
Arsenal's first European tie since the departure of talismanic striker Thierry Henry will be a tough one too, against Czech side Sparta Prague.
Scottish champions Celtic face a tough test against Spartak Moscow in their bid to reach the group stage.
Last season's SPL runners-up Rangers will face either 1991 European Cup winners Red Star Belgrade or Estonian side Levadia Tallinn if they overcome FK Zeta in the second qualifying round. They lead 2-0 from the home leg.
The first legs will be played on August 14 and 15, with the return matches taking place on August 28 and 29.
Toulouse reached the Champions League qualifiers by finishing third in Ligue 1 behind champions Lyon and runners-up Marseille.
They are coached by former Bordeaux boss Elie Baup and one of their star players is Sweden striker Johan Elmander, who was a reported target of Manchester City boss Sven-Goran Eriksson and also Lyon. He scored 11 times for the club, including a last-day hat-trick against Bordeaux.
Arsenal's opponents Sparta are the champions of the Czech Republic. Their success last season was their 34th domestic title and they became the first club since the break-up of Czechoslovakia in the early 1990s to win the domestic double.
Their best performance in Europe came in 1992-93, when they reached the semi-final group stage under an old format of the Champions League.