Calado last raced in a single-seater championship in 2013, when he finished third in the GP2 Series while holding a test driver role for the Force India Formula 1 team.
Following GP2, Calado began racing in the World Endurance Championship in the GTE Pro class, winning the championship in 2017 and taking a class win at Le Mans earlier this year.
"This was one of the most sought-after seats in Formula E and I’m extremely proud to have been offered it," Calado said. "Jaguar’s motorsport history is iconic and to be a part of this team in Formula E is a great opportunity for me.
"Although electric racing is new to me, I’m confident in my own single-seater experience to secure some great results for the team. Expectations are high and I can’t wait for the first race in Diriyah in November."
The announcement has squashed rumours that linked Nico Hulkenberg to the Jaguar seat, as the German is currently without a race drive in F1 for 2020.
Jaguar ended the 2018/19 season of Formula E seventh in the championship standings, picking up one race victory courtesy of Evans at the Rome ePrix.
"I would like to welcome James to the Panasonic Jaguar Racing Formula E team," said Jaguar team director James Barclay. "His experience in multiple formulas and outright pace will be a huge asset to the team.
"We learnt how to win as a team last season and we are hungry for more. To be successful in Formula E you need two drivers who can compete for podiums at every race. With Mitch and James we can look to build on the success of last season by securing even more points, podiums and wins."
Bahrain International Circuit - Winter testing
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