63-year-old Xi, regarded as the most powerful leader heading the party, military and the government, will complete his first five-year term during the 19th party Congress to be held later this year and start his second five-year term.
In CPC system, leaders have a 10-year tenure.
A total of 2,300 delegates to the National Congress, slated for the second half of 2017, are being elected by 40 electoral units across the country. The election will be completed by June.
The announcement of Xi's unanimous election won a burst of long and warm applause at the provincial congress, state- run Xinhua news agency reported.
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The unanimous vote of Xi by more than 730 provincial congress delegates represents the shared aspiration of more than 1.7 million CPC members in Guizhou and the wholehearted support of over 40 million residents, the delegates said.
The CPC national congress, which typically convenes once every five years, is of great importance. It hears and deliberates reports of the Central Committee and the Central Commission for Discipline Inspection.