The official Korean Central News Agency said the delegation was on "an official goodwill visit" to North Korea without elaborating, but Li's visit was widely seen as Beijing's last ditch bid to encourage Pyongyang back to six-party talks aimed at persuading it to abandon its nuclear ambitions.
The Chinese delegates were greeted by a group of North Korean ruling communist party leaders and cabinet officials, including vice foreign minister Kim Yong-Il, the agency said.
Li was accompanied by ranking officials, including vice foreign minister Wu Dawei, on a four-day visit to Pyongyang in a new drive in the quest to prevent the nuclear talks from derailing.
Talks are due to resume this month but prospects have been murky because of strained US-North Korean relations and embarrassing revelations of Seoul's previous nuclear research.
The new round is to bring together the two Koreas, the United States, Russia, Japan and China in Beijing by the end of September.
The stand-off flared in October 2002 when the United States accused Pyongyang of operating a nuclear weapons program based on enriched uranium, violating a 1994 agreement.
Pyongyang has denied running the uranium-based program but has restarted its plutonium program.