The event was streamed over the 5G network and broadcast on Facebook, Twitter and YouTube, the company said in a statement.
A 5G-powered performance was created in collaboration with Stormzy to celebrate the six cities that EE has connected with 5G.
More than 200 state-of-the-art LEDs were affixed to the stage, with beams of light projected 1000ft in front of the Tower Bridge.
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Fans in the other five launch cities were treated to the best seat in the house via a 360-degree VR experience at stores in Cardiff, Edinburgh, Belfast, Birmingham and Manchester.
BT Consumer division chief executive Marc Allera said: "We wanted to mark the arrival of the UK’s first 5G network with something spectacular.
"Tonight, we made history, not only by becoming the first network to launch 5G in the UK, but also by using 5G to livestream this event to thousands of fans across the UK.
"Stormzy lit up the Thames and his fans’ faces with the energy, passion and charisma that he always brings to his live shows.”
The company is selling smartphones from Samsung, OnePlus, LG, and OPPO, a mobile broadband device from HTC, and a 5G home broadband router from Huawei to consumers from today.
EE will also introduce 5G across the busiest parts of Bristol, Coventry, Glasgow, Hull, Leeds, Leicester, Liverpool, Newcastle, Nottingham and Sheffield.
In 2020, 10 more towns and cities will get 5G sites: Aberdeen, Bournemouth, Brighton, Cambridge, Dundee, Exeter, Ipswich, Norwich, Plymouth and York.