This study reports that small amounts of MoO3 multilayer ribbon crystal (MoO3 MLRC) in Ni3Al intermetallics showed the decreased friction coefficients and improved wear resistance at different contact loads. Specifically, the friction coefficients (0.32–0.34) and wear rates [(2–4) × 10−5 mm3 N−1 m−1] are significantly reduced for Ni3Al at 2–8 N. A possible explanation for the friction and wear reduction is that MoO3 MLRC as a multilayer material shears easily in the tribo-layer during the sliding contact, and provides low friction. In addition, this MoO3 MLRC with excellent bending strength is found to dissipate shear stress and suppress severe plastic deformation under a cyclic stress, thus drastically improving wear resistance of Ni3Al.