The 28-year-old world No 4 will likely face sixth-ranked Petra Kvitova and ninth-ranked Lucie Safarova, the left-handed duo who have led the Czechs to three Fed Cup titles from the last four editions.
"It's a great way to finish off the year playing with two of the best players," said Sharapova, a five-time Grand Slam winner, who was sidelined with leg and arm problems from July to October.
"It's definitely a very new experience. I've been part of the team on different occasions but never in the final."
Sharapova returned to action at the WTA Tour Finals last month, where she lost to Kvitova in the semifinals – after losing to Safarova at the French Open in June.
"I know how difficult an opponent they are and it will be a great challenge for me," said Sharapova, called up alongside 23rd-ranked Ekaterina Makarova, Anastasia Pavlyuchenkova (28) and Elena Vesnina (111).
"We are coming into these finals as the underdogs," she added.
