"It's a fantastic achievement, Gareth's been a great example for all players and is the epitome of a quality professional," said head coach Gareth Jenkins.
"He is a significant selection, his experience and enthusiasm is on display for everyone to see in training and he has a renewed sharpness and edge to his game that can only benefit this Wales team.
"You wouldn't bet against him breaking through the 100-caps barrier with two games on this tour, three summer matches and then the Rugby World Cup just around the corner.
"He was inspirational after missing the first four matches of the Six Nations this year and he leads a team bubbling with international experience into a match we are looking to win."
Thomas leads the charge from the right wing, with Chris Czekaj guarding the other flank, and the captain will be followed into battle by the new half-back pairing of scrum-half Mike Phillips and James Hook. Jamie Robinson and Sonny Parker form the centre partnership, with Robinson playing outside his New Zealand born colleague.
Colin Charvis is following fast on Thomas' heels with a similarly impressive 84-caps, and more than 10-years international experience, which he adds to a forward pack formed entirely from 20-cap plus players - save hooker Matthew Rees who has 10 appearances to his name.
Adam Jones and Iestyn Thomas make up the front row, alongside Rees, and Aussie native Brent Cockbain partners Rob Sidoli in the second row.
Gavin Thomas - the only other player apart from the captain to have scored a try against the Wallabies - joins blind-side flanker Charvis and No8 Jonathan Thomas to complete the back row.
Prop Ceri Jones and lock/back row Scott Morgan are the only uncapped players in the match-day squad and both provide cover from the bench.
"With Colin it's a case of us looking to him to reproduce his regional form on the international stage," said Jenkins.
"We are looking for players of his versatility, like Jonathan Thomas he is capable of covering each position in the back row and he is without doubt a player of outstanding ability who could put his hand up on this tour.
"Gavin (Henson) is another player we will need to have a close look at.
"We felt we needed to introduce him slowly, but he his likely to play a part in the game at some stage and we can further assess his progress then.
"He simply has to play rugby sooner or later and he has been going well in training, full of smiles and really helping to energise the squad.
"On a final note it was sad to find out Gareth Williams has to leave the tour, he too has made an impact with everyone and he will be bitterly disappointed to miss out.
"We now look forward to welcoming two hookers Mefin Davies and Steve Jones to the squad this Friday.
"This team has a huge incentive with Rugby World Cup squad places up for grabs.
"And both sides will be looking for victory in order to gain psychological advantage before we meet in the World Cup."
Wales: Lee Byrne; Gareth Thomas (Capt), Jamie Robinson, Sonny Parker, Chris Czekaj; James Hook, Mike Phillips; Iestyn Thomas, Matthew Rees, Adam Jones, Brent Cockbain, Rob Sidoli, Colin Charvis, Gavin Thomas, Jonathan Thomas
Replacement: Richard Hibbard, Ceri Jones, Michael Owen, Scott Morgan, Gareth Cooper, Ceri Sweeney, Gavin Henson.
15 Lee BYRNE (OSPREYS)
DoB: 01.06.80. 6'3" / 1.91m. 14st 4lbs / 91kgs
International record: 12 caps (W 3, L 8, D 1; 10 pts - 2T)
14 Gareth THOMAS (TOULOUSE - CAPTAIN)
DoB: 25.07.74. 6'2" / 1.88m. 16st 4lbs / 103kgs
International record: 92 caps (W 49, L 42, D 1; 185 pts - 37T)
13 Jamie ROBINSON (CARDIFF BLUES)
DoB: 07.04.80. 6'2" / 1.88m. 15st 0lbs / 95kgs
International record: 18 caps (W 6, L 12; 30 pts - 6T)
12 Sonny PARKER (OSPREYS)
DoB: 27.08.77. 6'1" 1.86m. 14st 4lbs / 91kgs
International record: 21 caps (W 11, L 10; 25 pts - 5T)
11 Chris CZEKAJ (CARDIFF BLUES)
DoB: 14.12.85. 6'3" / 1.91m. 15st 12lbs / 101kgs
International record: 4 caps (W 1, L 3; 5 pts - 1T)
10 James HOOK (OSPREYS)
DoB: 27.06.85. 6'0" / 1.83m. 12st 11lbs / 81kgs
International record: 11 caps (W 3, L 7, D 1; 81 pts - 3T, 15C, 11PG, 1DG)
9 Michael PHILLIPS (CARDIFF BLUES)
DoB: 29.08.82. 6'3" / 1.91m. 14st 0lbs / 89kgs
International record: 20 caps (W 10, L 9, D 1; 10 pts - 2T)
1 Adam Rhys JONES (OSPREYS)
DoB: 08.03.81. 6'0" / 1.83m. 19st 0lbs / 121kgs
International record: 40 caps (W 20, L 18, D 2; 5 pts - 1T)
2 Matthew REES (LLANELLI SCARLETS)
DoB: 09.12.80. 6'2" / 1.88m. 15st 11lbs / 100kgs
International record: 10 caps (W 3, L 6, D 1; 10 pts - 2T)
3 Iestyn THOMAS (LLANELLI SCARLETS)
DoB: 15.12.76. 6'1". 17st 3lbs
International record: 30 caps (W 10, L 20)
4 Brent COCKBAIN (OSPREYS)
DoB: 15.11.74. 6'8" / 2.04m. 18st 11lb / 119kgs
International record: 23 caps (W 13, L 10; 5 pts - 1T)
5 Robert SIDOLI (CARDIFF BLUES)
DoB: 21.06.79. 6'6" / 1.99m. 18st 2lbs / 115kgs
International record: 39 caps (W 17, L 21, D 1; 10 pts - 2T)
6 Colin CHARVIS (NEWPORT GWENT DRAGONS)
DoB: 27.12.72. 6'2". 16st 10lbs
International record: 84 caps (W 39, L 43, D 2; 100 pts - 20T)
7 Gavin Michael THOMAS (LLANELLI SCARLETS)
DoB: 22.10.77. 6'1" / 1.86m. 15st 10lbs / 100kgs
International record: 20 caps (W 7, L 13; 20 pts - 4T)
8 Jonathan THOMAS (OSPREYS)
DoB: 27.12.82. 6'5" / 1.96m. 16st 10lbs / 106kgs
International record: 32 caps (W 15, L 15, D 2; 30 pts - 6T)
16 Richard HIBBARD (OSPREYS)
DoB: 13.12.83. 6'0". 17st 4lbs
International record: 2 caps (L 2)
17 Ceri JONES
DoB: 19.06.77. 6'1" 16st 7lb
International record: uncapped
18 Michael OWEN (NEWPORT GWENT DRAGONS)
DoB: 07.11.80. 6'5" / 1.96m. 18st 2lbs / 115kgs
International record: 34 caps (W 17, L 16, D 1; 10 pts - 2T)
19 Scott MORGAN (CARDIFF BLUES)
DoB: 17.10.78. 6'6" / 1.99m. 17st 4lbs / 110kgs
International record: Uncapped
20 Gareth COOPER (NEWPORT GWENT DRAGONS)
DoB: 07.05.79. 5'7" / 1.71m. 13st 4lbs / 84kgs
International record: 32 caps (W 16, L 16; 30 pts - 6T)
21 Ceri SWEENEY (NEWPORT GWENT DRAGONS)
DoB: 21.01.80. 5'10" / 1.78m. 13st 7lbs / 86kgs
International record: 30 caps (W 15, L 15; 84 pts - 4T, 23C, 5PG, 1DG)
22 Gavin HENSON (OSPREYS)
DoB: 01.02.82. 6'0" / 1.83m. 15st 7lbs / 98kgs
International record: 20 caps (W 11, L 8, D 1; 130 pts - 3T,29C,18PG,1DG)