The leader is being recognized for his heroic defiance of Russian aggression.
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The ceremony takes place at the National Constitution Center in Old City.
Zelenskyy will not be at the ceremony but did record remarks.
Delaware Senator Chris Coons, who recently met with Zelenskyy, will speak Monday evening.
Organizers will also play recorded remarks from former President George W. Bush.
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The Liberty Medal award honors men and women of courage and conviction who strive to secure the blessings of liberty for people around the globe and is presented with a $100,000 prize.
Organizers say President Zelenskyy announced his plans to allocate the prize to the newly established Ukrainian Veteran Fund with the Ministry of Veteran Affairs of Ukraine.
Past recipients have included U.S. Supreme Court Justice Ruth Bader Ginsburg, U.S. Senator John McCain, U.S. Representative John Lewis, His Holiness the 14th Dalai Lama of Tibet and Malala Yousafzai.
The event begins at 6 p.m. For ticket information, visit the National Constitution Center's website.