In a video shared on Facebook, the actor can be seen smiling and waving at fans as she ordered a coffee.
Jolie has worked as a special envoy for the United Nations (UN) Refugee Agency for many years, but the specifics of her trip to Ukraine are unclear.
The video, which shows Jolie signing a piece of paper and waving to the camera, was posted on Facebook by Ukrainian Maya Pidhorodetska and has since had more than 19,000 shares.
Ms Pidhorodetska wrote a post with the video in Ukrainian which, translated by Google, said: “Nothing special. Just Lviv. I just went to have coffee. Just Angelina Jolie.
“Ukraine is simply supported by the whole world.”
Lviv, in western Ukraine, has been under attack from the Russian army in recent weeks and earlier this month, a missile attack on the city left at least seven people dead.
In February, Jolie spoke about the war in Ukraine in a post to her 12.7 million Instagram followers.
She wrote: “Like many of you, I’m praying for the people in Ukraine.
“My focus along with my @refugees colleagues is that everything possible is done to ensure the protection and basic human rights of those displaced, and refugees in the region.
“We have already seen reports of casualties and people starting to flee their homes to seek safety.
“It is too soon to know what will happen, but the significance of this moment – for the people of Ukraine, and for the international rule of law – cannot be overstated.”