Wang was at the frontline of Xi's anti-corruption crusade, heading the party's Central Commission for Discipline Inspection, which has punished 1.5 million officials in the past five years, from low-level cadres to regional leaders and generals.
Xi and Wang took the oath of office by pledging allegiance to the Constitution, into which the president's political thought was incorporated as the amendment of the country's supreme law was enacted for the first time since 2004 earlier this month.
Chinese President Xi Jinping was reappointed with no limit on the number of terms he can serve.
The move will solidify Xi's position who had the term limit for the president and vice president removed from the Constitution.
Xi's real power stems from his title as general secretary of the Communist Party, but analysts say Wang could provide extra heft to his presidency, even though the vice president has largely been a ceremonial post in the past. Wang, however got 2,969, one vote less in the carefully choreographed poll. He is the first Chinese leader to have that privilege after party founder Chairman Mao Zedong who ruled China from 1949 till his death in 1976.
Wang, who a year ago retired from China's elite Standing Committee which rules the country, spearheaded Xi's anti-corruption campaign, which has netted millions including high flying politicians for graft. According to reports, the observers claimed the vote share show diversity in China's political system.
"[I pledge to] be loyal to the country and the people, be committed and honest in my duty, accept the people's supervision and work for a great modern socialist country that is prosperous, strong, democratic, culturally advanced, harmonious, and attractive", said the president.
Last Sunday, parliament voted to amend the constitution, which removed presidential and vice-presidential term limits, meaning Xi can stay in power indefinitely. The parliament also ratified a new plan to revamp the government.
China has been trying to head off a trade war with the United States, sending envoys to Washington in recent weeks, including Xi's top economic advisor Liu He.
Later the NPC expected to elect the new premier, ministers and other top officials.
From India's perspective on the new line-up of officials, China's Foreign Minister Wang Yi was widely expected to be elevated to state councillor which makes him the top diplomat of the country.
The elevation will entail him to become China's special representative for India-China boundary talks.
Wang was a member of the Politburo Standing Committee, the Communist Party's top decision-making body, but stepped down in October due to a party norm that requires officials aged 68 and above to make way for younger generations.