The connected coffee shops include locations such as Westminster and Regent Street in London as well as outlets in Manchester, Birmingham and Glasgow.
The launch of the connections coincides with research commissioned by BT that highlights one in four workers (26 percent) head to a coffee shop at least once a week, to seek refuge from cramped offices that lack space and get on with some work without any distractions.
Chris Bruce, general manager, BT Openzone, said: "As costs for space increase, there's a clear trend for business people to leave cramped offices to hunt out a quiet coffee shop corner to work and hold meetings. As more customers bring along Wi-Fi-enabled devices, we aim to provide broadband connectivity wherever they are, making work something you do, not somewhere you go."
Jonathan Hart, managing director, Caffè Nero, added: "To make Caffé Nero even more 'work friendly' we have partnered with BT Openzone to offer Wi-Fi in all our stores."