Li arrived in Zagreb with a 250-strong delegation, continuing the intensive contacts between Beijing and Zagreb of recent years.
On Wednesday, he will meet with Prime Minister Andrej Plenkovic, President Kolinda Grabar-Kitarovic and Parliament Speaker Gordan Jandrokovic as well as sign numerous contracts.
"This is a big political message to Croatia and a chance for the Croatian economy," Plenkovic told reporters at Zagreb's airport ahead of Li's arrival.
On Thursday and Friday, Li will be in Dubrovnik at the eighth summit of 16+1, the format in which he will meet his counterparts from central and east Europe.
Regular summits have enabled smaller countries to build and develop relations with the world economic power with a population of more than 1.3 billion.
In recent years, China has started investing more in central and southeast Europe, considering the 16+1 initiative an integral part of its One Belt One Road project, a contemporary Silk Road and one of the most ambitious projects in the world.
Li arrived in Croatia after an EU-China summit in Brussels.
Text: Hina