Anabel Medina Garrigues helped Spain win the title last year and is returning for the defense, when she'll be partnered by two-time Hopman Cup champion Tommy Robredo.
Former U.S. Open champion Sam Stosur and Bernard Tomic will represent Australia, while Jo-Wilfried Tsonga and Alize Cornet will play for France.
Poland will make its debut in the tournament with a team containing No. 4-ranked Agnieszka Radwanska and Wimbledon semifinalist Jerzy Janowicz.
U.S. Open semifinalist Andreas Seppi will join Flavia Pennetta in the Italian team, and Milos Raonic will team up with Eugenie Bouchard for Canada.
"I think Hopman Cup is a great way to start the year. You have a lot of guaranteed matches, a lot of opportunities to find your way especially after the off season," Raonic said. "It gives you a chance to really get match sharp. It's a great competitive atmosphere, a team atmosphere, something different and something I haven't been involved in."