Scotland will face Poland in a friendly at Hampden Park on Thursday March 24, with GBP10 from every ticket sold going towards UNICEF’s Ukraine emergency fund.
The match replaces the World Cup play-off semi-final against Ukraine, which has been postponed until June due to the ongoing war.
Poland were also due to play their semi-final that day but will instead travel to Glasgow after FIFA threw opponents Russia out of the tournament as a sanction for the invasion.
Scotland will also face the loser of Austria or Wales, who meet in Cardiff, in an away friendly five days later.
Captain Andy Robertson said: “As a father, the images of children in Ukraine has been heart-breaking to watch.
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“I am a proud ambassador for UNICEF and when we were informed that the match against Ukraine would be postponed then working in partnership with Robert and the Polish squad to do our bit to help the situation was a no-brainer.
“We send our love and prayers to our fellow participants across Ukraine’s football community and hope that the money raised by this match will help the tremendous efforts already made by UNICEF in Ukraine and in helping the refugee situation.”
Head coach Steve Clarke – who will name his squad for the double-header on Tuesday – added: “We’ve seen wonderful examples of individuals and groups within Scottish football rally with their own contributions towards the situation in recent weeks.
“With the support of UNICEF, this match is a way for all Scottish football fans to unite in solidarity and support our friends in Ukraine.
“As many have already said, football is unimportant when you see the situation in Ukraine. I know that the Scotland supporters and the players will rally to show that the power of football can have a positive impact even during such desperate situations as the one faced in Ukraine at present.”
Scottish FA Chief Executive Ian Maxwell added: “It goes without saying that our thoughts are with the people of Ukraine. All football-related matters pale into insignificance next to what the people of that country are experiencing.
“Along with the counterparts at the Polish FA, we hope to use this friendly international as our chance to show solidarity with a country and its people, while raising as much money to help them as we can in the process.”
Shevchenko’s message to Russia: You can stop this war
Former Chelsea and AC Milan striker Andriy Shevchenko said football “doesn’t exist” for him amid the current invasion while speaking to Sky Sports News.
Shevchenko’s family have refused to leave Ukraine and the 45-year-old has remained in London during the conflict to help lead the appeal to get humanitarian aid to his country.
“Football doesn’t exist for me any more,” Shevchenko said.
“I don’t think about it. It’s not the time for that. I’m not watching anything, any sport, anything.
“All my concentration, when I wake up, I think about how I can help my country, what I can do. I’ve started to call my parents, my friends, get updates on what’s going on in Ukraine.
“For me, this is my field, this is my concentration now.”