The visit comes after President Vladimir Putin received Chinese leader Xi Jinping last month in Moscow for a summit showing the nations' united front against the West.
During a meeting with Russian counterpart Sergei Shoigu, Li said he wanted to demonstrate Beijing's "firm determination to strengthen the strategic cooperation between the armed forces of China and Russia," according to the defence ministry in Moscow.
Li's first overseas visit since taking over as China's defence minister comes amid fears in the West that Beijing could send weapons to boost Russia's offensive in Ukraine.
China's defence minister said the two countries would take military cooperation and trade "to the next level", the ministry said in a statement.
Shoigu called for the development of the Russia-China relationship to "strongly support each other, including on national security issues".
Russia's defence minister said it was "important that our countries see eye to eye on the issue of the ongoing transformation of the global geopolitical landscape".
Li was expected to stay in Moscow until Wednesday.
China has sought to position itself as a neutral party on the conflict, even as it has maintained close ties with Russia.
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