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Zao was born in Beijing with family roots in Dantu, Zhenjiang, Jiangsu province. In his childhood he was brought back to his hometown Dantu where he studied calligraphy. From 1935 to 1941, he studied painting at the China Academy of Art in Hangzhou, Zhejiang province, where he was taught by Lin Fengmian, Fang Ganmin and Wu Dayu. In 1948, he went with his wife Lan-lan, a composer, to Paris to live on the same block in Montparnasse where the classes of Émile Othon Friesz took place. His earliest exhibitions in France were met with praise from Joan Miró and Picasso.

Zao and his wife pursued their own careers, their son having stayed in China with Zao's parents. In the mid-1950s, they were divorced. In 1957, Zao decided to visit the United States where his younger brother Chao Wu-Wai was living in Montclair, New Jersey, close to the art scene of New York City. He wanted to learn more about "pop art". While in the US, he painted seven canvases at his brother’s house. There are relatively few items dating from that year (1957). Years later, the largest canvas was given by his brother, Chao Wu-Wai, to the Detroit Institute of Arts.[3]

He left the U.S. after a six-week stay, traveling to Tokyo and then to Hong Kong, where he met his second wife Chan May-Kan (陈美琴, May Zao), a film actress who had two children from her first marriage. Under the influence of Zao, she became a successful sculptor. In 1972, she committed suicide at age 41 due to mental illness.