Handpicked by Chung and the M&S design team, the collaboration will see archive pieces brought back to life for the modern age - with a supermodel twist.
The supporting campaign will launch, along with the clothes, in April with Chung herself taking creative ownership of the mood and direction.
"I have always had an affection for Marks & Spencer," Chung said of the partnership.
"I am thrilled to be part of this special and unique project. There was something very touching about looking back through the British fashion and social history for which M&S is synonymous."
This project is the first of the ‘M&S &’ series - a number of exclusive collections with some of today’s most exciting designers, brands and fashion icons.
The M&S & Alexa Chung collection will debut in April 2016 and will be available in selected stores and online at www.marksandspencer.com