The team of Juliya Dzhyma, Olena Pidhrushna and sisters Vita and Valj Semerenko finished the course 1 minute, 4 seconds ahead of Germany, whose team narrowly squeaked past third-place France.
Ukraine bolted into the lead in the final two stages of the relay after Germany's Franziska Hildebrand missed three shots and had to take a penalty loop. The German woman had taken the lead from faltering Belarus earlier Saturday, Russia's R-Sport said.
Saturday's race was one of only four women's relay stages this season. The next one takes place next week in France.