The two players came face to face in a light-hearted interview with The Players' Tribune where the pair were seen laughing and joking throughout.
Piqué even quizzed the 26-year-old over Cristiano Ronaldo's infamous birthday party back in 2015, where the Barcelona defender credited trap singer Kevin Roldán for Real Madrid's dip in form towards the back end of that season.
"You've come here to ask me about that?" James joked after being questioned about Roldan, quoted by Marca. "It didn't affect the dressing room at all."
The pair continued with the comical exchange before Piqué invited the Colombia international to move to the Camp Nou in the near future, insisting that James will fit the profile of players already at Barcelona.
James spent three years at Real Madrid after securing a move to the Santiago Bernabéu in the aftermath of his breakout performances at the World Cup in 2014.
But the former AS Monaco midfielder, who joined Los Blancos for £67.5m, was shipped out on a two-year loan to Bayern Munich last summer. The Bavarians can - and likely will - make the move permanent for just £37m at some point over the next season.
James was arguably Bayern's best player during his maiden campaign in the Bundesliga. He made 39 appearances across all competition as the Reds secured yet another league title, scoring eight goals and claiming 14 assists.