Scolari, who led Brazil to their fifth and most recent world title in 2002, took charge of his first game in his second spell as coach and handed Ronaldinho a recall for his 100th cap.
Ronaldinho had a 19th minute penalty saved at Wembley before Wayne Rooney and Frank Lampard scored to help England end a 23-year winless record against the Brazilians.
Seven minutes after Joe Hart saved the spot-kick, Rooney swept in a loose ball after Theo Walcott's shot was saved. Fred equalized in the 48th but substitute Lampard clinched victory for England, curling one in from the edge of the area.
Spain’s Pedro Rodriguez took his tally to nine goals in his last six internationals by scoring twice in the second half against Uruguay after Cesc Fabregas' 16th-minute opener was canceled out by Cristian Rodriguez in the 32nd.
Germany came back from behind to defeat France, whom Mathieu Valbuena headed in front just before half time. Thomas Muller equalised in the 51st and Sami Khedira scored 16 minutes from time to clinch Germany's first win over France in 26 years.
Sweden versus Argentina was billed as a head-to-head between Zlatan Ibrahimovic and Lionel Messi. Neither scored but Messi had the bigger impact and even a close encounter with a pitch invader, who embraced him and kissed him on the forehead.
Mikael Lustig turned in Gonzalo Higuain's shot for Argentina's opener before Sergio Aguero and Gonzalo Higuain added further goals after Jonas Olsson equalised. Rasmus Elm's free kick in injury time came too late for the hosts.
Cristiano Ronaldo scored for Portugal, who were beaten 3-2 at home to Ecuador. Italy, meanwhile, seemed on their way to a sixth straight friendly loss when Jeremain Lens put the Netherlands in front in the 33rd, only for Verratti to come off the bench and score a last-gasp equaliser.