The 55-times capped British and Irish Lions scrum-half will be the 124th player to captain Wales in 578 Tests. He will also be the 18th Llanelli Scarlets player to lead his country.
The side features three changes from that which faced Rugby World Cup hosts France at the Millennium Stadium last month with props Adam Jones and Gethin Jenkins replacing Duncan Jones and Chris Horsman in the front row. Squad captain Gareth Thomas is moved to the bench with his spot at inside centre taken up by Sonny Parker and Stephen Jones joins Thomas as a replacement after being declared fully fit and ready for action.
"Gareth (Thomas) put in three royal performances for us during August, but this is the first time Sonny Parker has been available to us to start a game so we are giving him a chance in the centre," said Jenkins.
"We have been saying for some time that we will use more than one captain during this tournament and Dwayne was always one of three players who will potentially captain the side at this World Cup alongside Gareth and Stephen.He is one of our identified leaders, a core member of the squad and the very definition of a professional rugby player.
"He will cope admirably with the responsibility of captaining his country. He follows in the footsteps of some great players and we know will do justice to the honour that has been bestowed upon him."
Eleven of Wales's starting line-up have previous world cup experience - with James Hook, Matthew Rees, Ian Gough and Alun-Wyn Jones the tournament debutants.
British Lion Michael Owen could also make his debut in the competition from the bench alongside hooker Rhys Thomas and scrum half Michael Phillips.With Colin Charvis, Stephen and Duncan Jones and Gareth Thomas all providing cover from the bench the Wales 22 boasts 63 World Cup appearances between them - and if Thomas comes on, he will become the outright Welsh record holder for RWC appearances with 12 (currently joint holder on 11 with Ieuan Evans).
"Canada will be tough first-up opponents for us, but we must concentrate on refining our own game and it is time now for everything to begin to click in to place," added Jenkins.
"We have been boosted by the news that Stephen Jones is fit again and raring to go and we will be hoping to give him some game time if the situation suits. We need to ask some questions of Sonny in the inside centre position and ensure that he has relevant game-time under his belt as we begin our campaign.If Gareth Thomas is struck down in training we need to know what we have available in that position.
"If we are going to be successful in this World Cup we will need to select from the talented bank of players we have at our disposal and we need to know we have the right personnel in place in the right positions to be able to contend with any eventuality.
"The combination of Adam and Gethin and Matthew is one that we have not tried through the summer and they have been given an opportunity to play together as a unit.
"We are absolutely clear this is going to be one of our toughest games. The Canadians have always represented themselves strongly in RWC tournaments, they have a lot of knowledge of us and they will have a tactical approach that will challenge us."
Wales Team to face Canada
15 Kevin Morgan (RWC record: 2 apps, 2003 - Canada, Italy)
14 Mark Jones (RWC record: 3 apps; 2T, 2003 - Canada (1T), Tonga, Italy (1T), England)
13 Tom Shanklin (RWC record: 2 apps, 2003 - Tonga, New Zealand)
12 Sonny Parker (RWC record: 3 apps; 3T, 2003 - Canada (1T), Italy (1T), New Zealand (1T))
11 Shane Williams (RWC record: 2 apps, 2003 - New Zealand, England)
10 James Hook
09 Dwayne Peel (C) (RWC record: 5 apps, 2003 - Canada*, Tonga*, Italy, New Zealand*, England*)
01 Gethin Jenkins (RWC record: 5 apps, 2003 - Canada, Tonga, Italy*, New Zealand*, England*)
02 Matthew Rees
03 Adam Jones (RWC record: 5 apps, 2003 - Canada*, Tonga*, Italy, New Zealand, England)
04 Ian Gough
05 Alun-Wyn Jones
06 Jonathan Thomas (RWC record: 3 apps, 2003 - Italy*, New Zealand, England)
07 Martyn Williams (RWC record: 6 apps; 3T, 1DG, 1999 - Japan, Samoa, 2003 - Canada, Tonga (1T, 1DG), Italy (1T), England* (1T))
08 Alix Popham (RWC record: 2 apps, 2003 - Tonga, New Zealand)
16 T Rhys Thomas (RWC record: 2 apps, 2003 - Canada, Italy)
17 Duncan Jones (RWC record: 7 apps; 4T, 1999 - Argentina (1T), Australia, 2003 - Canada (1T), Tonga, Italy, New Zealand (1T), England (1T))
18 Michael Owen
19 Colin Charvis (RWC record: 7 apps; 4T, 1999 - Argentina (1T), Australia, 2003 - Canada (1T), Tonga, Italy, New Zealand (1T), England (1T))
20 Michael Phillips
21 Stephen Jones (RWC record: 5 apps; 1T, 5C, 7PG, 1999 - Japan*, 2003 - Tonga (1C, 4PG), Italy*, New Zealand (4C, 3PG), England (1T))
22 Gareth Thomas (RWC record: 11 apps; 6T, 1995 - Japan (3T), New Zealand, Ireland, 1999 - Argentina, Japan* (1T), Samoa (1T), Australia, 2003 - Canada (1T), Italy, New Zealand*, England)