Company also looking at fingerprints, voice recognition and heartbeat to unlock money transfers.
Mastercard will be recruiting 500 UK customers to trial its pay-by-face this coming autumn.
Mastercard confirmed that it is closing a deal with two major banks, although the card payments provider has not chosen to disclose their names.
Apple, BlackBerry, Google, Microsoft and Samsung have all signed up for their devices to be used in trials.
Customers using the facial recognition solution will have to hold their phones in front of their faces, blink once and wait for the scan to convert the information into ones and zeros.
This data will then be transferred to Mastercard who will allow card payments or money transfers.
Expanding its biometric offering, Mastercard will also enable customers to use fingerprint authentification via a downloadable app.
The company said the data will be kept on its own servers and plans to make a full launch of the service once the system is secure.
Ajay Bhalla, Mastercard’s President of Enterprise Safety and Security, said: "The new generation, which is into selfies … I think they’ll find it cool. They’ll embrace it."
Robert M. Lee, co-founder of Dragos Security, said: "From a privacy aspect it’s awful — but from a business perspective, I don’t understand why they’d accept that risk."
MasterCard confirmed that is also looking at the introduction of voice recognition and is already working with Nymi to use a person’s heartbeat in a future version of the app.