"Now I announce comrade Xi Jinping is selected as president of the People's Republic of China," said Liu Yunshan, a top official of the ruling party who chaired the electoral session at the National People's Congress.
To loud applause, Xi, 59, stood up and bowed to the delegates gathered in the Great Hall of the People, before shaking hands with other officials and walking off the stage.
The announcement came after the delegates to China's rubber-stamp parliament cast red ballot papers in a leadership vote where the outcome was never in doubt.
Li Yuanchao, a member of the Communist Party's Politburo but not among its top seven-member Standing Committee and a figure seen as having reformist leanings, was selected as vice-president, Liu said.
China's vice-presidency is a largely symbolic post, although it does carry a diplomatic role.