James scored twice in her international debut for Wales last November against Sweden and has impressed Wales coach Jason Lewis since being brought into the squad.
"I've no qualms about giving Caryl her chance at this level," said Lewis. "She is a level headed person and an experienced sportsperson and has taken to international rugby well.
"I'm happy with the squad we've chosen. We've got more depth within the squad than we had this time last year and selection has been much more difficult, particularly in the front five where we are blessed with talent at the moment," added Lewis.
Current Six Nations champions England will go into the match firm favourites, having beaten the mighty New Zealand side emphatically at Twickenham in November.
"You've got to give England credit," said Lewis. "They are constantly one or two in the world and by beating New Zealand they've proved just how good they are. We are under no illusions as to the size of the task which confronts us but we are delighted to have the opportunity of taking them on in our first game of the campaign."
With the World Cup to be staged later in the year, all sides will be jockeying for position which should add extra spice to this year's Six Nations according to Lewis.
Elsewhere, in a largely settled squad, hooker Becky Newton, centre Ceri Redman and fly half Elinor Snowsill have come through the age grade system to force their way into the Six Nations squad for the first time, with the trio having played in last season's Under 20s side. They will all start the game from the bench.
Wales Women (v England, Esher RFC, Saturday 6th Feb, 7pm KO)
15 Non Evans - Cardiff Quins
14 Aimee Young - UWIC
13 Naomi Thomas - Cardiff Quins
12 Clare Flowers - Bristol Ladies
11 Caryl James - Cardiff Quins
10 Awen Thomas - Unattached
9 Amy Day - Bristol Ladies
1 Catrin Edwards - Cardiff Quins
2 Jenny Davies - Waterloo
3 Hannah Roberts - UWIC
4 Gemma Hallett - Pontyclun
5 Rachel Taylor - Cardiff Quins
6 Catrina Nicholas - Cardiff Quins
8 Mellissa Berry - Blaydon (captain)
7 Jamie Kift - Bristol Ladies
Substitutes
16 Clare Horgan (Saracens) 17 Becky Newton (Cardiff Quins) 18 Claire Donovan (Saracens) 19 Louise Horgan (Saracens) 20 Laura Prosser (Cardiff Quins) 21 Elinor Snowsill (Loughborough) 22 Ceri Redman (UWIC)

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