Rozner completes the Continental Europe team being captained by Francesco Molinari while Mansell joins Great Britain and Ireland line up being skippered by Tommy Fleetwood.
The event, which takes place in Abu Dhabi from 13-15 January, has been introduced to help Donald and potential team members prepare for the Ryder Cup in Rome next September.
The former world No 1 had left one position vacant in both teams for players to impress in the final stages of the DP World Tour calendar season.
Rozner secured his spot after claiming a third DP World Tour title as he claimed a five-shot victory at the AfrAsia Bank Mauritius Open on Sunday.
Mansell, meanwhile, made the most of his playing opportunities in 2022 as he regained full playing privileges after finishing 44th on the rankings.
Donald said: “We have a fantastic mix of major champions and Ryder Cup players, alongside those who are hoping to secure their debut for Team Europe in Rome next September, and the Hero Cup will provide me with a fantastic opportunity to see how these players adapt and react in a team environment.”
The event takes place at Abu Dhabi Golf Club and Dr Pawan Munjal, Chairman and CEO, Hero MotoCorp, said: “This unique event with an innovative format brings together 20 of the most talented golfers from Europe for an exciting match-play contest. We look forward to a week of world class golf.”