Officials noted that the call took place after Medevedev spoke over the weekend to Ukraine's new prime minister Arseniy Yatsenyuk, but did not give further details.
"The vice president urged Russia to pull back its forces, support the immediate deployment of international monitors to Ukraine, and begin a meaningful political dialogue with the Ukrainian government," a White House statement said.
Biden held repeated conversations with ousted Ukranian president Viktor Yanukovych throughout Ukraine's political crisis and has continued his role as a US conduit to Ukraine's interim government.