Olena Iurkovska won bronze on the first morning of competition, just hours after Ukraine's Paralympics team decided to attend the 10-day event despite Russia's military occupation of the nearby Crimean peninsula.
Iurkovska finished third in the women's six-kilometre sitting competition. Svetlana Konovalova of Russia took silver.
"I devote my first medal in Sochi to an independent Ukraine," Iurkovska said. "Every time I race, it will be for Ukrainian independence and peace in my country."
Iurkovska embraced Valentina Matvienko, the speaker of Russia's upper house of parliament, at the post-event flower ceremony.
Later Saturday, Ukraine won two more bronze medals in the biathlon, while Maksym Yarovyi claimed silver in the men's 7.5-kilometre sitting event and Vitaliy Lukyanenko took gold in the visually impaired class.
The crisis in Ukraine has overshadowed the second phase of Russian president Vladimir Putin's bid to use the Winter Games to polish his country's image abroad. Russia's military intervention in Crimea, about 475 kilometres west of Sochi on the Black Sea coast, began after the closing ceremonies of the Olympics two weeks ago.
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