Ian Cable will only accept payment via the Barclays PingIt app during the five-day trial, following on from also being the first cabbie to use chip and pin as a form of payment back in 2004.
"I am very excited to take part in this trial. I have been a cabbie for many years and am always up for trying new technology to help make mine and my passengers' lives easier. I was the first black cab driver in London to accept chip and pin back in 2004 and I will be the first to trial only accepting payment by Barclays Pingit", said Mr Cable.
"Not only is the app convenient for my passengers, because they don't need to worry about getting cash out, it means I have more time on the road to earn money - rather than stopping off at the bank to pay in my earnings or pulling up at ATMs for passengers with the risk of getting a hefty parking fine".
According to a prediction by the the Centre for Economic and Business Research, by 2020, 20 million adults will use their smartphones to pay for goods.
Darren Foulds, director of Barclays Mobile and Pingit at Barclays, said: "We are always keen to support new ways to make people's lives easier. This Pingit trial in a London black cab really demonstrates the huge potential for mobile payments as they gain more widespread use."
During the trial, passengers who climb into Mr Cable's black cab will be able to make a Pingit payment by using the QR code reader built into the app, and scanning a unique code inside the taxi. The app works for anyone, regardless of who they bank with, so non-Barclays customers will also be able to take advantage of the trial.
The mobile payment app was launched in 2012, and has since been used to transfer more than £500 million.