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The Lightning Seeds will take to the stage for a one-off show at the Eurovision Village in Liverpool.
The free gig on 10 May, which will also include Miles Kane, Girls Don't Sync and Michael Aldag, will help "meet the demand" from fans, the National Lottery and Music Venue Trust (MVT) said.
It is part of the United By Music Tour which is taking place across Merseyside to support grassroots venues.
Lead singer Ian Broudie said he was "delighted" to support the campaign.
The city is preparing to host the UK's first Eurovision for more than 20 years, which will see two semi-finals and a final take place at the M&S Bank Arena between 9 and 13 May.
Tickets to the 15,000-capacity 10 May gig will not be sold in advance and fans will need to arrive at Liverpool's Pier Head by midday with spaces assigned on a first come first served basis, organisers said.
The show starts at 18:30 BST but there will be a "range of performances in the build-up to the evening show", including appearances from some of the acts competing in Eurovision 2023.
Ian Broudie said it was "incredible" to "play a part in providing Liverpool with a whole week of music".
"We are delighted to be supporting a campaign that is backing so many music venues across Liverpool, one of the world's leading cities for music."
There will be gigs across Liverpool to "showcase the city's music scene" and to "support the grassroots music venues that remain the lifeblood of UK music", organisers said.
They start on Monday and feature artists from Liverpool, including The Coral, Jamie Webster, Crawlers and The Mysterines, and indie rocker Kane.
Mark Davyd, chief executive of MVT, said the charity was "completely blown away" by the response to the United by Music events, which sold out in four minutes.
He said:"Liverpool is still the home of live music and we simply couldn't meet the demand from local audiences [so we] found a way to bring even more music to Liverpool".
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