Belgium bounced back from the heavy loss to the Netherlands by thrashing Poland 6-1 at the Stade Roi Baudouin.
The Red Devils were eager to get back to winning ways after a 4-1 loss to the Netherlands last week, while Poland defeated Wales on the same day.
The visitors broke the deadlock in the 28th minute, with talisman Robert Lewandowski finding the back of the net after being set up by Sebastian Szymanski.
Roberto Martinez's men managed to pull level three minutes before the break courtesy of a fine strike by Axel Witsel.
Belgium took over in the second half, as a brace from Leandro Trossard and further strikes from Kevin de Bruyne, Leander Dendoncker and Lois Openda wrapped up the big win.
The Netherlands maintained their winning start in Group 4 after defeating Wales 1-0 at Cardiff City Stadium.
Gareth Bale was only named on the bench after the World Cup play-off win on Sunday, as Brennan Johnson was recalled in the attack.
The game's opening goal fell to the visitors five minutes after the halftime break thanks to Teun Koopmeiners' finish.
Wales looked to have clinched a point when Rhys Norrington-Davies equalised in the 92nd minute, but Wout Weghorst bagged the winning goal for the Dutch two minutes later.
Scotland began their Nations League campaign with a 2-0 win over Armenia on Wednesday night.
The home side broke the deadlock on 28 minutes through Anthony Ralston's strike, before Scott McKenna doubled the lead five minutes before the break.
Ukraine bounced back from the World Cup play-off loss to defeat the Republic of Ireland 1-0 at the Avivia Stadium.
Viktor Tsyhankov bagged the only goal of the game two minutes after the halftime break.
