Between 1961 and 1963 Marvin made three movies with John Wayne. They were:

The Comancheros (1961), as Tully Crow, the head of a band of renegade arms merchants and thieves known as Comancheros.

The Man Who Shot Liberty Valance (1962), as Liberty Valance where Marvin played his first title role and held his own with two of the screen's biggest stars (Wayne and James Stewart).

Donovan's Reef (1963), as Thomas Aloysius 'Boats' Gilhooley,a drunken hooligan and decorated Marine that stayed in the South Seas. This was his largest role to date.

More Info: en.wikipedia.org