Speculation and media reports have swirled for the past week that Xi would snub the event, but China had remained silent on the issue.
US President Joe Biden has said he would be "disappointed" to see Xi skip the gathering of world leaders in New Delhi.
Beijing's foreign ministry confirmed Monday that Li would be at the G20 Leaders' Summit on Saturday and Sunday, which it described as an important forum for economic cooperation.
"In attending this meeting, Premier Li Qiang will convey China's thoughts and positions on G20 cooperation, pushing for the G20 to strengthen unity and cooperation, and working together to combat global economic and development challenges," spokeswoman Mao Ning told a regular news briefing.
Asked whether the announcement meant Xi would not travel to New Delhi, Mao said: "I made an announcement about this just now. Premier Li Qiang will lead a delegation to New Delhi, India, to take part in the G20 Leaders' Summit."
The Group of 20 major economies consists of 19 countries and the European Union, making up about 85 percent of global GDP and two-thirds of the world's population.
The summit has taken on additional importance this year as many countries wrestle with high inflation and economic turbulence amid a slowing recovery from the Covid-19 pandemic.
China, the world's second-largest economy, has set an annual growth target of around five percent but has its own problems including weak consumer demand, soaring youth unemployment and a crisis in the crucial property sector.
Asked about Xi reportedly not planning to join the gathering in New Delhi, Biden told reporters on Sunday: "I am disappointed, but I am going to get to see him", without elaborating.
Xi has attended every G20 summit since coming to power except Rome in 2021, when he participated by video link.
- BRICS pivot? -
Xi's likely absence from New Delhi stands in contrast to his grand reception at a key summit of major developing economies last month.
The Johannesburg meeting of the so-called BRICS nations -- Brazil, Russia, India, China and South Africa -- saw the Chinese President take centre stage as six new countries were admitted into the bloc.
Argentina, Ethiopia, Iran, Saudi Arabia, Egypt and the United Arab Emirates will become full members from January 1, in a decision that Xi hailed as "historic".
"The expansion is also a new starting point for BRICS cooperation. It will bring new vigour to the BRICS cooperation mechanism and further strengthen the force for world peace and development," Xi said at the time.
China has long campaigned to expand and strengthen BRICS as a counterweight to US and Western dominance of world affairs, especially as tensions have grown over technology, trade, human rights and other issues.
Beijing also has a long-running border dispute with G20 host nation India, with deadly brawls breaking out along their contested boundary in recent years.
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