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The actor, 56, was pictured in the large south-eastern city of Rzeszow, close to the border, speaking to aid workers in a storage facility.
Millions have crossed over into Poland since the war began in February.
— Ben Stiller (@BenStiller) June 18, 2022
He said: “I’ve just arrived in Poland with UNHCR, to meet families whose lives have been torn apart by war and violence in Ukraine.
“Millions have been forced to flee their homes with over 90% being women and children.
“I’m here to learn, to share stories that illustrate the human impact of war and to amplify calls for solidarity.
“I hope you’ll follow along and share your own messages of support, for people who have fled their homes in Ukraine and for people who have been forced to flee all over the world.
“Everyone has the right to seek safety. Whoever, wherever, whenever.”
Zoolander and Night At The Museum star Stiller’s presence in Poland comes ahead of World Refugee Day on June 20.
He started working with the UNHCR in 2016 and has travelled with the body to meet refugees in Germany, Jordan, Guatemala and Lebanon.
He is not the first celebrity to involve themselves in humanitarian work for Ukraine, with Mila Kunis and Ashton Kutcher raising 35 million US dollars for the country and David Beckham handing over his Instagram page to a Ukrainian doctor in Kharkiv for the day.