They will be joined by Emeli Sande, Gregory Porter and Snow Patrol at the fundraising gig, which will take place at the Resorts World Arena in Birmingham and air live on ITV tonight (Tuesday) at 8pm.
Also taking to the stage are Paloma Faith, Nile Rodgers & Chic, Becky Hill, The Kingdom Choir, Manic Street Preachers and Tom Odell.
The show is set to be hosted by Roman Kemp, Marvin Humes and Emma Bunton.
Cabello said: “My heart is breaking for the people of Ukraine. As refugees from Ukraine join millions of other displaced people around the globe, we all have a responsibility. One of the biggest needs is to get funds to organisations who can serve these communities directly, so we’re focusing our efforts on doing that as quickly as we can.”
Russian president Vladimir Putin began his military invasion of Ukraine on 24 February. Cities in the country have suffered mass destruction and hundreds of thousands of Ukrainians have fled the country.
Sheeran - who is currently caught up in a copyright lawsuit at the High Court over his song 'Shape Of You' - did not release a statement.
Sande commented: “I will be singing to try to help every human being forced to flee their home and in solidarity with those being racially discriminated against even within this humanitarian crisis. Nobody should be refused access to relief, aid and the right to cross the border to safety, and I’m pleased for the chance to support the DEC’s appeal to help all people whose lives have been affected by the conflict.”
And Gregory Porter added: "So thankful to be able to raise my voice in the chorus of peace. Together we can show our support for those that are sadly affected by the current world's events.”
The broadcast will combine musical performances with short films recognising the ongoing relief efforts and the difficulties faced by those affected by the conflict.
Viewers will be invited to donate money to the DEC [Disasters Emergency Committee] Ukraine Humanitarian Appeal throughout the two hour evening show.
All sponsorship and advertising revenue generated from the broadcast – estimated to be more than £3 million – will also be donated to the DEC appeal.
Concert For Ukraine will be broadcast on ITV, STV, ITV Hub and STV Player.
ITV has previously supported DEC appeals including for the Afghanistan crisis in December 2021.
Concert for Ukraine airs at 8pm tonight (Tuesday) on ITV.
Watch: Ed Sheeran recently took the witness stand in a copyright lawsuit