Pitt settled down with the Jolie and they were considered a rare Hollywood success.
The pair fell in love after starring alongside one another in Mr and Mrs Smith.
But the power couple called time on their 12 year relationship with Jolie filing for a divorce on Monday.
So from Jolie to Aniston and Sinitta we took a look at Pitt’s relationship history.
He went on to formally adopt her two adopted children Maddox and Zahara after only two years of dating.
The A-lister, 52, enjoyed a succession of relationships after his role in Thelma and Louise catapulted him to stardom in the early 1990s.Brad and Jennifer had 200 guests, over 50,000 flowers, a gospel choir, four bands, and fireworks at their wedding reception. Their wedding rings were designed by Brad Pitt and were matching white gold bands decorated with small diamonds.