Footage of Jolie's visit has been shared on social media, with the star appearing to greet fans as she entered a coffee shop in the city.
News of Jolie's presence in Ukraine comes as Vladimir Putin's invasion of the country continues.
Sharing a clip of the Maleficent star on her Instagram stories, journalist Maya Pidhorodetska wrote, as reported by the Daily Mail: "Nothing special. Just Lviv. I just went to have coffee. Just Angelina Jolie."
"Ukraine is simply supported by the whole world," she continued.
In the footage, which has since been shared further on Twitter, Jolie appears to sign her autograph before continuing through the coffee shop.
A tweet has also been shared showing the actor meeting refugees from Donbas.
Meeting the refugees from Donbas 🙏🏼 pic.twitter.com/uDEbHuSWky— Tanya Kozyreva (@TanyaKozyreva) April 30, 2022
People had mixed reactions to the star's visit, with one user writing: "Why not just send financial assistance (I know she's probably done so), but her visit will more than likely just be an inconvenience. Imagine all the logistics, manpower & security to keep her comfortable & safe. So unnecessary IMO."
Another added: "So thousands are flocking from a war, yet Hollywoods Elite are popping over for a visit... right, got ya."
But others, on the other hand, supported Jolie's visit, with one saying: "Another great woman to join other great fighting women. Does anybody doubt our future will be run by women? I love it."
With another saying: "It's so nice that international guests still come to Ukraine. Symbol picture is the best example of trust... Angelina Jolie good luck."
While it is not yet clear what Jolie will be doing in Ukraine, she has previously spoken out in support of the country, taking to social media to share her thoughts.
On 24 February, the mother of six took said via Instagram: "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."
If you would like to donate to the Red Cross Emergency Appeal, which will help provide food, medicines and basic medical supplies, shelter and water to those in Ukraine, click here for more information