Measures include cutting high debt, streamlining state-owned enterprises, and reforming financial markets.
China has been facing a period of slower growth and market volatility.
The plan, laid out by Communist Party leaders, received unanimous approval from delegates at the largely rubber-stamp NPC.
At his annual press conference later, Mr Li stressed the importance of reforms to economic vitality.
He acknowledged there would be job losses as reforms were made to state-owned enterprises, particularly in the steel and coal industries, but said there would be no mass redundancies.
The economy would "not suffer a hard landing, we have full confidence in the bright future of the Chinese economy".
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