The wear tests of titanium matrix composites (TMCs) at the loads of 50, 100, 120, and 150 N were carried out with an MMW-1 vertical universal friction and wear tester to study the addition of multilayer graphene (MLG)/nano-Fe2O3 composites (0, 0.1, 0.2, 0.3, 0.4, and 0.5 g) on the dry sliding wear behavior of TMCs. TMCs presented a marked variation in wear loss as a function of the amount of MLG/Fe2O3 addition, and a significant decrease in the friction coefficient was obtained, reducing this parameter up to 50%. With the rise and fall of wear loss, TMCs underwent a transition from severe wear to mild wear. These phenomena were attributed to the existence of a protective lubricating film, which prevented the surface from coming in direct contact, and the lubricating film was 15–20 μm thick and made up of MLG/Fe2O3 (1:2) nanocomposites. Its structure was speculated to be similar to a rolling wood.