The Russian Ministry of Foreign Affairs summoned the U.S. Ambassador to protest the decision to label Putin a war criminal.
According to a statement from the Foreign Ministry, Sullivan was told that Biden's accusation had put Russian-American relations on the verge of breakdown.
Biden said March 16 that he believes Putin is a war criminal. It was Biden's first time branding Putin with that phrase.
The International Criminal Court's top prosecutor met with top officials from Ukraine hours after Biden's comment.
A State Department spokesman did not respond to CNBC's request for comment.
Sullivan was asked to stay on by the U.S. president at the start of Biden's first term.
As Russia nears the one-month point in its invasion of Ukraine, the diplomatic breakdown comes.
An initial Russian infantry advance has largely stopped outside of the major cities. This has forced the Kremlin to shift tactics from a quick land war to a war of attrition marked by the shelling of residential areas in an effort to wear down and demoralize the nation.
White House press secretary Jen Psaki later said that Biden was speaking from his heart about what he had seen on the news.
There is a legal process to determine if Putin has committed war crimes. She said that the process is underway at the State Department.
While the formal process proceeds slowly, top officials in the Biden administration have openly alleged that Putin is a war criminal and that Russia is committing war crimes in Ukraine.
The Secretary of State agreed with the president's assessment of Putin.
Intentionally targeting civilians is a war crime. After all the destruction of the past three weeks, it's hard to conclude that the Russians are not doing anything.