Champions Liverpool, Manchester United, Inter Milan, Ajax Amsterdam - with 13 European Cups between them - along with AS Monaco, Panathinaikos and Sporting add some heavyweight class to the competition, with the first legs being played on Tuesday and Wednesday.
Liverpool have been there from the start and need to get past Bulgarian champions CSKA Sofia to reach the group stage having taken advantage so far of UEFA's decision to install them in the competition despite not qualifying by finishing in the top four of the Premier League.
CSKA knocked Liverpool out in 1982 when the English club were the holders but are unlikely to repeat the feat.
Liverpool were edged out of fourth place by city rivals Everton, who consequently return to the European Cup for the first time since 1971 having been denied twice in the 1980s because of the ban on English clubs following the Heysel Stadium disaster.
Everton take on Villarreal, third in the Spanish league last season and also in the Champions League for the first time, in one of the most attractive ties of the round, with the first leg at Goodison Park.
Villarreal will be spearheaded by Uruguay striker Diego Forlan, who struggled to make an impact while at Manchester United but finished as the top scorer in Spain last season with 25 goals.
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United, the third English team in the qualifying round, play Hungarian champions Debrecen, hoping to join Chelsea and Arsenal in the group stages as for the first time in the competition's history one country has five entrants.
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Monaco, runners up in 2004, are struggling for form ahead of their visit to Spanish Cup holders Real Betis in Seville on Tuesday.
Didier Deschamps' side lost 2-0 at home to AJ Auxerre on Saturday having struggled past Nancy 1-0 on the opening weekend of French league action.
Inter Milan, who ended a 16-year domestic drought by winning the Italian Cup in June, have to look back 40 years for the last of their two European Cup triumphs.
They have been overshadowed by city rivals AC, who were beaten on penalties by Liverpool in last season's final, and need to get past Ukraine's Shakhtar Donetsk to join them in the group stage this year.
They will do so without Italy striker Christian Vieri, who moved to AC Milan last month, but with former world and European player of the year Luis Figo, who joined from Real Madrid last week.
Steaua Bucharest, the 1986 European champions, face Norway's Rosenborg Trondheim. The Champions League regulars, who won the Norwegian title for the 13th consecutive time last season, are finding it hard going in the current campaign in their worst run of form since the 1970s.
With nine matches remaining they are in the bottom half of the table after losing eight games, including a 5-1 thrashing by Fredrikstad last Wednesday and a 2-1 home defeat by Lillestrom on Sunday that led to coach Per Joar Hansen resigining.
Swiss outsiders Thun, who knocked out Dynamo Kiev in the last round, face Malmo, third in the Swedish league.
Four-times European champions Ajax begin at Danish double winners Brondby, Panathinaikos visit Wisla Krakow while Sporting host Udinese in Lisbon.
The second legs of the ties will be played on 23/24 August, with the losers going into the UEFA Cup.
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