James is the fifth uncapped player named in the squad alongside Jacob Beetham and Ellis Bevan (both Cardiff Rugby), Keelan Giles (Ospreys) and Josh Hathaway (Gloucester Rugby).
Wales face South Africa in an away fixture at Twickenham Stadium on 22 June before heading for Australia on 26 June to play two Test matches against the Wallabies and a fixture against the Queensland Reds.
An updated squad of 34 players who will travel to Australia will be confirmed following the Springboks encounter.