The US card company has rolled out the technology in the UK and 11 other European countries including Spain, Germany and Finland.
To access the new function, customers must download the new Identity Check Mobile app, through which they can authorise payment with a fingerpringt or face recognition.
The service requires users to take a selfie with their mobile device and upload their photo to Mastercard, which then creates a digital map of their face, ready to be used when a purchase needs to be verified.
The credit card firm has been testing selfie software in the US, Canada and Netherlands. Some 92 per cent of test subjects preferred the new system to passwords.
Some security researchers have said that biometric checks have the potential to cut fraud, but others have warned that they might not be as secure as traditional methods.
Of those who tested the software, 83 per cent said it was more secure than passwords.
Ajay Bhalla, president, enterprise risk and security, Mastercard, said the initiative is a “significant milestone” in the evolution of payments.
“Shopping in person has been revolutionized thanks to advances like contactless cards, mobile payments and wearables, and now we are making Identity Check Mobile a reality for online shopping in Europe, and soon, the world," he said.
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