Former Ireland skipper Best is calling time on a 15-year senior career after Saturday's match at Twickenham.
It has now been confirmed the 37-year-old will lead Eddie Jones' side, with the England coach having also included three of South Africa's Rugby World Cup winners.
Makazole Mapimpi and loosehead prop Tendai Mtawarira – also making the final appearance of his career – start, with Lukhanyo Am named on the bench.
In total, there are 10 South African players within the 23-man invitational squad.
