The US president briefly confused the two when he described the importance of providing humanitarian aid to countries torn apart by civil war.
Mr Biden was also discussing how he might work with Russia’s president, Vladimir Putin, as the two prepare to meet face-to-face in Geneva on Wednesday.
Their encounter will come at a moment when relations between Moscow and Washington are strained. Mr Biden has repeatedly criticised his opposite number over allegations of Russian interference in the 2020 election and the hacking of federal agencies in what is known as the SolarWinds breach.
On Sunday, Mr Biden told reporters: “We can work together with Russia, for example, in Libya. We should open the passes to be able to go through, provide food assistance and economic assistance, vital assistance to a population that’s in real trouble.
“Russia has engaged in activities which we believe are contrary to international norms, but they have also bitten off some real problems they’re going to have trouble chewing on.
“For example, the rebuilding of Syria, of Libya, they’re there, and as long as they’re there without the ability to bring about some order in the region, and you can’t do that very well without providing for the basic economic needs of people.
“I’m hopeful that we can find an accommodation where we can save the lives of people, for example, in Libya.”
Russia has backed Syria’s dictatorial president, Bashar al-Assad, in that country’s brutal, decade-long civil war. Moscow has been accused of targeting civilian sites, including hospitals, for airstrikes.
Russia and Western powers have both engaged in military intervention in Libya over the last decade.