The two-hour Concert for Ukraine was organised to raise money for the Disasters Emergency Committee (DEC) and its response to the Russian invasion.
It also featured the country’s 2016 Eurovision winner.
The evening at the Resorts World Arena featured a star-studded line-up also including Camila Cabello, Anne-Marie and Gregory Porter – and was punctuated by short video pieces documenting the lives of displaced Ukrainians both inside and outside the country.
At the end of the night, the hosts announced that ticket sales, advertising, sponsorship and donations had led to the grand total, but it was expected to continue rising.
Sheeran took to the stage solo for a two-song set of his hits Perfect and Bad Habits.
Between the tracks, he told the audience: ‘Thank you so much for coming. It’s such an important cause and I am so honoured to be here.’
He was forced to pause briefly as he began his second song, admitting light-heartedly ‘I’ve got the wrong guitar’.
After making a quick change he resumed the show, to cheers from the crowds.
Pop superstar Cabello was backed by a string section for a performance of Coldplay’s hit Fix You before she was joined by Sheeran for a live debut of their new track Bam Bam.
She told the crowd: ‘We are praying tonight for the peace and safety of the people in the Ukraine.’
Ukrainian Eurovision winner Jamala, whose real name is Susana Jamaladinova, took to the stage after fleeing her home country following the invasion.
The 38-year-old delivered a rendition of her song 1944, about the forced deportation in Crimea during the rule of Joseph Stalin.
She waved a Ukrainian flag throughout her performance and was dressed in red.
Emma Bunton, one of the hosts, appeared visibly moved by her song.
‘Wow, thank you so much for Jamala for being with us and representing Ukraine during this very special concert here tonight – incredible,’ she said.
Jamala previously said her close friends and family remain in a bomb shelter in the Ukrainian capital of Kyiv.
The evening was host hosted by Roman Kemp, Marvin Humes and Spice Girls star Bunton in front of screens showing the sunflower, Ukraine’s national flower.
Welsh rock band Manic Street Preachers delivered an impassioned performance of their song If You Tolerate This Your Children Will Be Next, which has lyrics inspired by the Spanish Civil War.
There was also a performance from singer-songwriter Tom Odell, who recently went to the Romanian capital of Bucharest where he performed his hit Another Love for refugees arriving by train in the city.
Veteran broadcaster and journalist Sir Trevor McDonald appeared on stage to highlight the work of journalists reporting from the front line of the war.
Presenter and actress Mel Giedroyc, whose father fled Poland as a refugee during the Second World War, had fronted a short film at the Ukraine-Romania border which was shown to the audience.
Emotional, she said history was ‘repeating’ itself.
There were also video messages from Billie Eilish and her brother and collaborator Finneas O’Connell.
All sponsorship and advertising revenue generated from the broadcast were donated by ITV to the DEC appeal.