Kvyat raced in F1 as part of the Red Bull stable for six years between 2014 and 2020 at Scuderia Toro Rosso/Alpha Tauri and Red Bull Racing, securing three podium finishes.
Since then, he has made three outings in the NASCAR Cup Series last year, and sits second in the FIA World Endurance Championship's LMP2 category this season.
"I’m really excited to be trying the Formula E car for the first time ever and with NIO 333 Racing," said Kvyat. "I think Formula E has proved for many years to be a very competitive, high-level championship, with very interesting environmental goals as well.
"The racing is very fast, and very competitive. The team has also been making a lot of progress, especially this year, and has room to grow and fight for even stronger positions in the future. It’ll be interesting to see what we can do together at this test.
Spaniard Mikel Azcona will appear alongside Kvyat in the sister ER9 at the test. The touring car specialist won the WTCR FIA World Touring Car Cup last year, and is a twice European touring car champion in TCR Europe.
Azcona also spent two seasons competing in the FIA ETCR eTouring Car World Cup, where he was a three-time event winner in the electric touring car series, which featured rear-wheel drive EVs competing at up to 500kW of power.
"It’s a really nice feeling to be at the Rookie Test, and I’m very grateful for the opportunity that NIO 333 has given me," said Azcona. "It’s something new for me in my career, and it’s my first time driving a single-seater since 2012. So I really want to improve my skills there, and I really want to learn about this new technology.
"It’s going to be interesting seeing what I can bring from my time in electric touring car racing, which was also new to me, but where I was very competitive. Some of the technology is similar in theory, but I’m expecting it to be quite something else when I get into the Formula E car."