Ospreys prop gets the nod after Gethin Jenkins fails a fitness test on a calf problem picked up in training.
The injury has forced Jenkins to withdraw from the RBS 6 Nations clash with England at Twickenham on Saturday afternoon.
James' inclusion takes the number of Ospreys in the starting line-up to seven, with Adam Jones, Alun-Wyn Jones, Ryan Jones, James Hook, Shane Williams and Lee Byrne also featuring.
The uncapped Rhondda-born Saracens prop Rhys Gill takes up the spot vacated by James on the bench.
"Paul James has been one of the form props in the Welsh regions so far this season and we are confident he will be a more than able deputy for Gethin," said Wales head coach Warren Gatland.
"Obviously it's not ideal for us to lose Gethin at this stage and we wish him a speedy recovery."
Jenkins will remain in the Wales camp and his injury will be re-assessed next week.
Paul JAMES (OSPREYS - Cap No 1,021)
DoB: 13.05.82. 6'1" / 1.86m. 17st 7lbs / 111kgs
International record: 5 caps (W 3, L 2)
Rhys GILL (SARACENS)
DOB: 30.10.86 - Rhondda Valley
Ht: 1.80m (5'11") / Wt: 109kgs (17st 2lb)
International Record: Uncapped