Team GB will be without British No. 1 Johanna Konta as a long-standing knee issue means she struggles to adjust to new surfaces.
With the WTA Tour about to go into the clay-court swing, Konta did not want to return to an indoor hard court.
British No. 2 Watson is the highest-ranked player in the squad and is joined by Katie Boulter, who has a impressive record in the team tournament, with Harriet Dart, Katie Swan and Jodie Burrage completing the group.
The tie takes place at the National Tennis Centre from 16-17 April and a win will see GB advance to a one-off qualifier with the chance to make it to the 2022 Billie Jean King Cup Finals.
Team captain Anne Keothavong said: ‘I’m pleased to be able to announce the squad for this tie and I’m really looking forward to everyone linking up again.
‘Heather has shown great commitment to the team and the competition over the years and Katie Boulter and Harriet Dart have both shown their character in recent ties as well.
‘Along with Katie Swan and Jodie Burrage, we have a strong group of players who I’m confident can do us proud.
‘We all know the LTA’s National Tennis Centre very well and we’re looking forward to a competitive tie in familiar surroundings – and hopefully we can advance to the 2022 finals.’