Djokovic and Bale's team, led by Ryder Cup icon Colin Montgomerie (60), came out on top in the contest against Corey Pavin's (63) outfit.
"It's a great honour, I want to thank the Ryder Cup for giving me this once-in-a-lifetime opportunity... it's a unique experience," said Djokovic, who won a record-equalling 24th Grand Slam title at the US Open earlier this month.
His highlight at the Marco Simone Golf and Country Club was driving through the par-four 16th green.
"The crowd made me do it and I'm really happy they did," added Djokovic, who played alongside disability golf world number one Kipp Popert (25).
Former footballer Bale, who was often criticised by fans for playing too much golf while at Real Madrid, won his match alongside Montgomerie against the Scot's fellow 2010 Ryder Cup captain Pavin and AC Milan attacking great Andriy Shevchenko.
"It (playing golf) is similar to a free-kick, to a penalty. I was a free-kick taker... So it definitely helps," said Bale.
Actor Kathryn Newton, former Super Bowl winner Victor Cruz (36) and Formula 1 driver Carlos Sainz (29) also took part.
