Cain was the son of Robert Cain, who had founded a large brewing empire, Robert Cain & Sons Ltd. He was educated at Winwick Priory. The family firm was taken over as joint managing directors by William Cain and his brother, Charles Nall-Cain, who continued to develop the business.
During the First World War, Cain donated his old home, Wilton Manor at West Kirby, to the government as a convalescent hospital for officers and paid for its conversion and equipment. He also donated money to many other war charities. For these services, he was knighted in 1917 and created a baronet in the 1920 New Year Honours.
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