Biggar will skipper the squad in the absence of the injured Alun Wyn Jones, with Adam Beard named as vice-captain.
And Pivac said: "In terms of captaincy we’ve named Dan Biggar.
"With the experience missing with some players out injured, we wanted someone who had experienced the competition on a number of occasions and knows the rigours of it.
"He gives us that – he has 95 Wales caps and he’s toured with the British and Irish Lions.
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“Dan has the respect of the other players and management so we think he’ll do a great job.”
The Wales squad will meet up at the national training base in Hensol on Monday, January 24 ahead of the first game, against Ireland at the Aviva Stadium in Dublin, on Saturday, February 5.
Wales' Six Nations squad
Forwards
Rhys Carre (Cardiff Rugby – 16 caps)
Wyn Jones (Scarlets – 38 caps)
Gareth Thomas (Ospreys – 5 caps)
Ryan Elias (Scarlets – 23 caps)
Dewi Lake (Ospreys – uncapped)
Bradley Roberts (Ulster Rugby – 1 cap)
Leon Brown (Dragons – 16 caps)
Tomas Francis (Ospreys – 60 caps)
Dillon Lewis (Cardiff Rugby – 34 caps)
Adam Beard (Ospreys – 29 caps), vice-captain
Ben Carter (Dragons – 5 caps)
Seb Davies (Cardiff Rugby – 13 caps)
Will Rowlands (Dragons – 13 caps)
Christ Tshiunza (Exeter Chiefs – 2 caps)
Taine Basham (Dragons – 7 caps)
Ellis Jenkins (Cardiff Rugby – 14 caps)
Jac Morgan (Ospreys – uncapped)
Ross Moriarty (Dragons – 49 caps)
James Ratti – (Cardiff Rugby – uncapped)
Aaron Wainwright (Dragons – 34 caps)
Backs
Gareth Davies (Scarlets – 65 caps)
Kieran Hardy (Scarlets – 8 caps)
Tomos Williams (Cardiff Rugby – 29 caps)
Gareth Anscombe (Ospreys – 29 caps)
Dan Biggar (Saints – 95 caps), captain
Rhys Priestland (Cardiff Rugby – 52 caps)
Callum Sheedy (Bristol Bears – 13 caps)
Jonathan Davies (Scarlets – 93 caps)
Uilisi Halaholo (Cardiff Rugby – 9 caps)
Nick Tompkins (Saracens – 16 caps)
Owen Watkin (Ospreys – 26 caps)
Josh Adams (Cardiff Rugby – 35 caps)
Alex Cuthbert (Ospreys – 48 caps)
Louis Rees-Zammit (Gloucester Rugby – 12 caps)
Johnny McNicholl (Scarlets – 8 caps)
Liam Williams (Scarlets – 74 caps)