He received his undergraduate education at Augsburg College in Minnesota and the University of Michigan
Wiley was the Republican candidate for governor of Wisconsin in 1936 but his bid failed. Philip La Follette and the new Wisconsin Progressive Party, which split from the Republicans in 1934, won the election. In 1938 Wiley was elected to the U.S. Senate by defeating incumbent F. Ryan Duffy. In 1944, he was challenged by Marine Captain Joseph McCarthy in the Republican Party primary. He defeated McCarthy and went on to win the general election. Wiley was re-elected two more times in 1950 and 1956. In 1956, he was challenged by Congressman Glenn Robert Davis in the Republican primary, but once again prevailed. In 1962, Wiley lost his bid for a fifth term to Governor Gaylord Nelson.