It comes as Russian forces started a renewed assault in the east of the country.
Lviv, where Angelina was pictured, is in Western Ukraine, around 80 kilometres from the Polish border.
The war-torn city has faced Russian shelling in recent weeks.
Angelina has visited war zones before, and previously worked with the United Nations Refugee Agency (UNHCR) to provide aid to Yemen last month.
Angelina has been working with the UN for years, after being appointed the position of Special Envoy to the United Nations High Commissioner for Refugees in 2012.
