Manchester City, Manchester United, Liverpool, Tottenham and Chelsea all qualified from their respective groups, making England the first country to have five teams in the competition's last 16.
Chelsea face a daunting tie, with Paris St Germain, Barcelona and Besiktas their only possible opponents when the draw is made at UEFA's headquarters at 11am GMT.
The Blues finished second behind Roma in their group and along with the Serie A side, they are also ineligible to face their Premier League rivals.
The two Manchester clubs, Liverpool and Tottenham all finished top of their groups, meaning Chelsea can only be paired with either the French or Turkish champions, or the current LaLiga leaders.
Chelsea did not qualify for last season's Champions League but their interest in the competition was ended by PSG in the previous two editions, although they eliminated Barca en route to the 2012 title in the last meeting between the teams.
For the four remaining English clubs, five-time champions Bayern Munich and last year's runners-up Juventus are stand-out dangers, while reigning champions Real Madrid are potential foes for United, City and Liverpool
Tottenham surprisingly finished ahead of the 12-time champions in the group en route to qualifying for the knockout stages for only the third time in their history, meaning they avoid Zinedine Zidane's men for the time being
Real defeated United in the European Super Cup earlier this year and have knocked the Red Devils out of the Champions League on three occasions since the turn of the century
Liverpool overcame Real in the 1981 European Cup final and memorably defeated them 5-0 on aggregate in the last 16 eight years ago
City are winless in their four meetings with Spain's capital club in the last five years
Basel, runners-up to United, Sevilla, second in their group to Liverpool, Shakhtar Donetsk, who qualified alongside City in their pool, and Porto will be viewed as kinder draws
PSG - bolstered by an enviable attacking trio of Neymar, Edinson Cavani and Kylian Mbappe - are currently favourites with bookmakers to go all the way in the Champions League for the first time
They could be paired alongside Real - third favourites behind Manchester City - in what would be indisputably the tie of the round
The draw for the last 32 of the Europa League will be conducted an hour later, and Arsenal, the only remaining English team in the competition, could face Scottish champions Celtic
Arsene Wenger's men will be seeded after finishing as one of 12 group winners and will therefore avoid the likes of AC Milan, Villarreal and Zenit St Petersburg
They will also be kept away from CSKA Moscow, Atletico Madrid, RB Leipzig and Sporting Lisbon, the four best third-placed teams in the Champions League group stages
Because Celtic won only won one Champions League game, they join Napoli, Spartak Moscow and Borussia Dortmund as the unseeded teams
Source : PA