Ukrainian officials have long been calling on Beijing to use its influence in Russia to help end the war.
China now appears to be stepping in, a year into the war in Ukraine, sensing that the West is not as unified as it appears.
Xi hass sought to position China as a potential mediator in the conflict but is seen by the West as favoring Russia.
Blinken said China's political and material support for Russia goes against Washington's interests.
"There was a very thorough exchange of views, a serious conversation in the informal part," the Kremlin spokesperson said, referring to Monday's meeting.
Xi was expected to press Beijing's role as a potential peacemaker in the conflict following the release of a 12-point plan
Reports say that the sides will discuss Russian-Chinese cooperation in the international arena. Important bilateral documents are supposed to be signed or at least come out of these meetings.
Xi has been seeking to present China as a global peacemaker and project it as a responsible great power.
The US has been engaging in suppression and containment of China rather than fair or rule-based competition, Foreign Minister Qin Gang stated on Tuesday.
Zelensky on Friday welcomed some elements of a Chinese proposal for a ceasefire in Russia's war on Ukraine.