Mr Li, arrived in India on Sunday afternoon on a three-day state visit, and Manmohan Singh are also likely to discuss the proposed border defence cooperation agreement during their talks, sources said on Saturday.
Mr Li's visit comes days after the 20-day India-China border stand-off was resolved on May 5. A platoon of Chinese troops had made incursions inside the Line of Actual Control (LAC) - the disputed border - on April 15 and pitched tents. The row was resolved after several rounds of negotiations - military as well as diplomatic - with both sides reverting to the position that existed before April 15.
China proposed a border defence cooperation agreement on May 5, and India has made some suggestions to be included in the draft.
Talks are on-going on the draft, said the source, adding "it will continue to be discussed".
The draft "essentially consolidates and brings together" earlier protocols and agreements.
Everything would be on the table when the two premiers meet, said the source, adding they are very likely to discuss the border issue.
The trade imbalance would also figure in talks. India is to press for market access in pharmaceuticals and IT. Bilateral trade was $66 billion last year as China became India's second-largest trading partner.
However, the trade imbalance stands at $28.87 billion, which is in favour of China.
Both sides are also expected to discuss regional and international issues, including Afghanistan.
Mr Li arrived on Sunday afternoon, and in the evening he is to meet Manmohan Singh for restricted level talks, and also attend a dinner hosted by the Indian prime minister. On Monday, he will be accorded a ceremonial reception at Rashtrapati Bhavan and also visit Rajghat to offer tributes.
He will then hold delegation level talks with the prime minister at Hyderabad House after which the two sides are expected to ink some agreements. The prime minister will host a lunch for the Chinese premier.
External Affairs Minister Salman Khurshid and Leader of Opposition in the Lok Sabha Sushma Swaraj will also be meeting him. Mr Li will call upon Vice President Hamid Ansari and UPA chairperson Sonia Gandhi.
On Tuesday, he will address an event at the Taj Palace Hotel being hosted by the Indian Council of World Affairs (ICWA) and FICCI and then proceed to Mumbai.
In the afternoon, Mr Li would visit the TCS office and also meet with the relatives of Dwarkanath Kotnis, an Indian doctor who is warmly remembered in China for his services during the second Sino-Japanese war (1937-1945).
In the evening, he is to address a dinner meeting of the three business chambers - Assocham, FICCI and CII.
Ahead of his arrival, the Chinese premier has already indicated the direction his interactions would take by hearkening back to his visit to this country 27 years ago and saying the fond memories of that trip have had a "lasting effect" on him.
Addressing an Indian youth delegation in Beijing ahead of his India visit, Mr Li said he has chosen India as his first foreign stop as prime minister, "not just because India is an important neighbour and one of the populous countries of the world but also because of the seeds of friendship sown during my own youth".
The premier has also signalled China's intent to see India-China ties at a higher level so that they can "together raise the standing of Asia in the world and truly make Asian economy an important engine for the world economy".
He will travel to Pakistan from India and then on to Switzerland and Germany on his nine-day trip.