Arsenal, Chelsea, Manchester City and Manchester United will find out their Champions League group stage rivals when the draw is made on Thursday.
Chelsea are in pot one alongside fellow seeds Barcelona, Bayern Munich, Benfica, Juventus, Paris St Germain, Zenit St Petersburg and PSV Eindhoven.
Arsenal, City and United are in pot two, along with Real Madrid, Atletico Madrid, Porto and Valencia.
The 32 teams in the draw will be put into eight groups of four.
In a change to previous seasons, pot one will be made up of holders Barcelona and league winners of the top seven European leagues – Spain, England, Germany, Italy, Portugal, France and Russia – rather than being based on club co-efficients.
As Spanish side Barcelona won last season’s competition, Dutch champions PSV go into the top pot as Netherlands are the eighth-ranked association.
A team from each of the four pots will be drawn into the eight groups, with no more than one team from any one country in each group.
Five star Spain
Spain are the first nation to have five teams qualify for the Champions League group stages this season.
Valencia beat Monaco in a Champions League qualifying play-off to reach the last 32 and they joined Atletico Madrid, Barcelona, Real Madrid and Sevilla, who qualified as Europa League winners.
Spanish teams have won four of the last seven Champions League, with Barcelona defeating Juventus in May’s final.
Spain also lead Uefa’s club coefficient rankings – the system used to decide which leagues get most qualifying spots for its competitions – by a considerable margin.
Van Gaal to watch second string
Manchester United have returned to the group stages following a one-season absence from the Champions League.
One: Barcelona, Bayern Munich, Benfica, Chelsea , Juventus, Paris St. Germain, Zenit, PSV Eindhoven
Two: Arsenal , Atletico Madrid, Bayer Leverkusen, Manchester City , Manchester United , Real Madrid, Porto, Valencia
Three: CSKA Moscow, Dynamo Kiev, Lyon, Olympiakos, Galatasaray, Roma, Shakhtar Donetsk, Sevilla
Four: Astana, BATE Borisov, Borussia Monchengladbach, Wolfsburg, Dinamo Zagreb, Maccabi Tel-Aviv, Gent, Malmo
The live draw stars at 15:45GMT in Monaco. Catch updates on Ultimate 106.9fm both on-air and online.