Webb – who played a major role on his first Lions tour in 2017 – is now eligible for selection and has been named one of three scrum-halves following the announcement he will re-join Ospreys next season.
Faletau has been absent from international rugby since March 2018 and gets the chance to showcase the form that earned him 13 Lions appearances.
Lions pedigree is prominent through the Wales team, with skipper Alun Wyn Jones, Ken Owens, Ross Moriarty, Justin Tipuric, Dan Biggar, George North, Leigh Halfpenny and Liam Williams also featuring.
Pivac insists he can’t wait to get his first taste of Six Nations action.
“We are really excited to be naming our Six Nations squad and kicking the campaign off,” he said.
“All of the coaches have been out and about, seeing players in training, speaking with them and we are pretty excited with the group we have got.
“Looking back to the Barbarians week, that was hugely important for us. We got a lot of ‘firsts’ out of the way. Getting to meet and get in front of the players and having a game together was hugely beneficial.
“We do have a couple of injuries, but we flip that into seeing it as an opportunity for some new players to impress, with not only the Six Nations in mind but also longer term and 2023.
“The Six Nations is hugely exciting for me. It is something I grew up watching from afar and it has such history attached to it, I’m really looking forward to the campaign.”
A string of injuries to the likes of Jonathan Davies have opened up opportunities for five uncapped players.
Prop WillGriff John, second-row Will Rowlands, centre Nick Tompkins and back-three duo Johnny McNicholl and Louis Rees-Zammit will all look to make their mark in the 2020 Championship.
Rhys Carre (Saracens) – 6 Caps
Rob Evans (Scarlets) – 36 Caps
Wyn Jones (Scarlets) – 22 Caps
Elliot Dee (Dragons) – 29 Caps
Ryan Elias (Scarlets) – 9 Caps
Ken Owens (Scarlets) – 73 Caps
Leon Brown (Dragons) -6 Caps
WillGriff John (Sale) – uncapped
Dillon Lewis (Blues) – 22 Caps
Jake Ball (Scarlets) – 42 Caps
Adam Beard (Ospreys) – 20 Caps
Seb Davies (Blues) – 7 Caps
Alun Wyn Jones (Ospreys) CAPTAIN – 134 Caps
Will Rowlands (Wasps) – uncapped
Cory Hill (Dragons) – 24 Caps
Aaron Shingler (Scarlets) – 26 Caps
Aaron Wainwright (Dragons) – 18 Caps
Taulupe Faletau (Bath) – 72 Caps
Ross Moriarty (Dragons) – 41 Caps
Josh Navidi (Blues) – 23 Caps
Justin Tipuric (Osprey) – 72 Caps
Gareth Davies (Scarlets) – 51 Caps
Rhys Webb (Toulon) – 31 Caps
Tomos Williams (Blues) – 16 Caps
Dan Biggar (Northampton) – 79 Caps
Owen Williams (Gloucester) – 3 Caps
Jarrod Evans (Blues) – 3 Caps
Hadleigh Parkes (Scarlets) – 25 Caps
Nick Tompkins (Saracens) – uncapped
Owen Watkin (Ospreys) – 22 Caps
George North (Ospreys) – 91 Caps
Josh Adams (Blues) – 21 Caps
Owen Lane (Blues) – 2 Caps
Johnny McNicholl (Scarlets) – uncapped
Louis Rees-Zammit (Gloucester) – uncapped
Jonah Holmes (Leicester Tigers) – 3 Caps
Leigh Halfpenny (Scarlets) – 85 Caps
Liam Williams (Saracens) – 62 Caps