He opened the Libbey Glass Co in Toledo, Ohio, in 1888, sponsoring a demonstration plant at the Chicago exposition of 1893. His success depended heavily on the inventions of Michael Joseph Owens. In 1903, Libbey founded the Owens Bottle Machine Company (later Owens-Illinois), and, in 1916, the Libbey-Owens Sheet Glass Company, serving as president of both firms.
He was the founder of the Toledo Museum of Art in 1901, serving as its president from 1901 to 1925, funding building construction, and bequeathing to the museum his collection of Dutch and English art. Libbey High School in Toledo, Ohio, was named after him.