Defending champion Tyrrell Hatton will reunite with actor Jamie Dornan as he returns to St Andrews on Thursday.
The Englishman played alongside Northern Irishman Dornan on his way to a first European Tour title last year, with the duo starting on the Old Course at 11.12 on Thursday.
Rory McIlroy will play in the company of his father, Gerry, at 09.22 as the four-time Major Champion aims to better his three previous runner-up finishes in the event.
Former champion Lee Westwood is set to tee it up with singer Ronan Keating at 11.23, 14 years on from his last victory here.
Westwood’s Ryder Cup teammate Graeme McDowell will play with retired jockey AP McCoy at 09.44, the duo now a regular pairing in the annual Pro-Am event.
Padraig Harrington and JP McManus will aim to win the team competition for a record third time and begin at 09.55.
Martin Kaymer will continue his run of playing alongside family and is partnered by his brother, Philip, this year after playing with father, Horst, in 2016.
Sky Sports pundit and former Liverpool footballer Jamie Redknapp will join Luke Donald at 10.17.
Ricardo Gouveia will tee it up alongside compatriot Luis Figo at 09.00 at Carnoustie’s Championship Course, with Callum Shinkwin and former England cricketer Kevin Pietersen under way on the same course at 09.33.