The Ukrainian capital is the first stop on Li's five-nation European tour, including Poland, France, Germany and Russia, as he seeks a "political solution" to the Ukraine crisis, according to China's foreign ministry.
Earlier, Reuters also reported that China's special representative for Eurasian affairs would be in Kiev on Tuesday and Wednesday, citing a Ukrainian government source.
Li's visit comes three weeks after Chinese President Xi Jinping promised Ukrainian President Volodymyr Zelenskyy that he would send a special envoy to Kiev.
Ahead of Mr. Li's visit, European Commission President Ursula von der Leyen stressed that Ukraine should lay out core principles for any solution.
The head of the EU's executive branch referred to the 10-point peace plan proposed by Zelenskyy in November, which included demands for Russia to withdraw its troops, restore safety around the Zaporizhzhia nuclear power plant, and restore Ukraine's national border with Russia.
The EU has been calling on China to play a more active role in helping end the conflict in Ukraine. In an interview with the Washington Post on Saturday, the EU's top diplomat Josep Borrell called Mr. Li's trip "a new step forward for China", following an April 26 phone call between Mr. Xi and Mr. Zelenskyy.
In February, China proposed its own Ukraine peace plan, which focuses on finding a "political solution" through negotiations.
China's foreign ministry said the delegation led by Li, China's former ambassador to Russia from 2009 to 2019, was "another demonstration of Beijing's commitment to promoting peace and negotiation".
Chinese Foreign Minister Qin Gang discussed the war in Ukraine when he visited France and Germany last week, pledging to strengthen cooperation with France to "solve global challenges".
Hoang Nam (according to TASS, Bloomberg, SCMP)