Massenet left Net-a-Porter when it merged with Yoox Group.
According to reports, the BFC chairman could be poised to re-enter the world of luxury e-commerce.
“Natalie is truly a trailblazer of the 21st century,” Nicholas Kirkwood said.
Yoox Group confirms Massenet’s resignation.
The move follows the site’s deal with Yoox.com earlier this year.