Profits from ticket sales and an estimated £3 million in advertising revenue from ITV will also be donated, with the concert raising more than £13.4 million in total.
The overall total of £260 million also includes £25 million matched by the UK Government at the start of the appeal.
The evening at the Resorts World Arena featured a star-studded line-up that also included Paloma Faith, Anne-Marie and Gregory Porter – and was punctuated by short video pieces documenting the lives of displaced Ukrainians both inside and outside the country.
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.”
‘I'm dancing in the dark with you between my arms’ 🥰
The one and only @edsheeran is stealing our hearts tonight… https://t.co/4M3ANcLNXY
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.