Kvitova, last year's Wimbledon champion and the winner of this year's U.S. Open series, moved into her second final of the season with a 6-1, 6-3 decision over Sara Errani. Kvitova was a winner two weeks ago in Montreal, where she captured her eighth career title.
Kirilenko won the opening set against four-time defending New Haven champion Carolina Wozniacki 7-5 and then advanced when Wozniacki withdrew with a right knee injury.
It was Wozniacki's first career loss at the Connecticut Tennis Center after winning 20 consecutive matches in the event.
Kirilenko has a 3-2 career edge over Kvitova, including a victory in the quarterfinals of the Olympics earlier this month in London.
Scarlett Johansson steps out with fiance after pregnancy reveal
Susan Sarandon 'very excited' about daughter's pregnancy