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Pep Guardiola's side bounced back from 0-2 to win 4-2 at the Etihad Stadium.
Real will take on RB Leipzig, Shakhtar Donetsk and Celtic in the group stage.
The record seven-time winner is missing out for the first time since 2005.
English champions City started their big close-season signing, Norway's Erling Haaland but, in contrast to Nunez, he had a disappointing debut, missing several chances and struggling to combine with his new team mates.
Spanish media reports that the transfer would cost Barcelona some 50 million euros ($50.4 million).
The Big Six in have all been busy with many high profile exits and entries on the horizon.
City did not provide financial details of the deal but German media reported that the total cost of buying Haaland could exceed 300 million euros ($314.22 million), including his salary, agent fees and bonuses.
Germany deservedly led through Jonas Hofmann's 50th-minute effort but were unable to finish England off and Kane levelled in the 88th minute after being tripped in the area.
Mbappe, who turned down Real and signed a new three-year deal at PSG last month, topped the list with an estimated transfer value of 205.6 million euros ($219.5 million), beating Vinicius (185.3 million euros) and Haaland (152.6 million euros).
With this win, Jose Mourinho became the first manager to win a European trophy with four different clubs.