The 32-year-old, who played in Bath's 30-16 European Challenge Cup defeat to Northampton on Friday, has been selected to play in Warren Gatland's senior trial match at the end of the month after a stellar campaign in England.
James, who has won 53 international caps and made five appearances for Wales during their 2014 RBS 6 Nations campaign, will line up alongside Bath team-mate Gavin Henson in the Possibles squad that will take on a Probables team at the Liberty Stadium in Swansea on May 30 and is confident of making the final squad to face the Springboks.
"Obviously an aim of mine was to make the tour and if I do I'll be over the moon," the former Ospreys forward told BBC Sport.
"There's no better place to go than South Africa to test yourself as an international. We'll see what happens.
"I've played well this season and played well last season. If they're picking a team on form and a squad on form hopefully I'll be alright."