He taught high school history at Delphi and Muncie, Indiana, and Springfield, Illinois, before receiving his PhD from the University of Wisconsin–Madison in 1925.

Buley authored numerous articles, reviews, and books, winning the 1951 Pulitzer Prize for History for his 2-volume work The Old Northwest: Pioneer Period 1815–1840 (1950).

Noted for always having an open door to students who wished to chat, in 1962 Indiana University's Sigma Delta Chi journalism society presented him the Brown Derby Award for being the most popular professor on campus.

No mere pedagogue, Buley took a broad view of education, as he expressed in The Old Northwest: Pioneer Period 1815–1840: "Much has been made, perhaps too much, of the illiteracy of the pioneer, of the lack of schools, and of the general backwardness of the southern emigrants in comparison with the eastern.

As James Hall said: 'A human being may know how to read, and yet be a very stupid fellow.... Reading and writing are not magic arts; of themselves, they are of little value... and thousands of individuals with diplomas in their pockets are far inferior, in point of common sense and information, to the common run of backwoodsmen.