Mexico is the third stop on a tour of Latin American and Caribbean nations that has already taken Xi to oil-rich Trinidad and Tobago, and Costa Rica, as Beijing looks to boost its trade ties in the region.
At week's end, he travels to the United States for a much-anticipated summit with US President Barack Obama.
After a formal welcoming ceremony at the Campo Marte military field, Xi was due to hold talks with Mexican President Enrique Pena Nieto, their second meeting in two months after Pena Nieto's trip to Beijing in April.
Observers say Pena Nieto's trip to China, which came just four months after he took office, showed his desire to cast aside old trade rivalries in favor of a closer partnership.
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China is Mexico's second-largest trading partner after the United States, and Mexico is Latin America's second largest economy after Brazil. Both countries are members of the Group of 20 leading economies.
The two sides are expected to sign 10 agreements in fields such as trade, investments, infrastructure, science and education.
But Mexico also wants to narrow a gaping trade deficit heavily tilted in China's favor: Mexico imported USD 57 billion worth of Chinese imports last year while exporting just USD 5.7 billion, according to the Mexican central bank.
Xi, who arrived in Mexico after visiting Trinidad and Tobago and Costa Rica, suggested that China was willing to work with Mexico to reduce the gap.
"The Chinese side has never intentionally sought surplus in bilateral trade," he said in comments carried by China's Xinhua news agency.
China, he added, "is ready to join in efforts with the Mexican side to tap into potential, expand the scale and optimize the structure of bilateral trade and seek balance of trade in an active way."