Deformation mechanisms especially grain boundary(GB)-related plastic behaviors are essential for understanding and designing advanced hard coatings. This work systematically studied mechanical behaviors and the underlying interfacial mechanisms in Ti-Mo-N coatings, which is predicted to have both high hardness and toughness according to first-principle calculation. Mo-doped TiN coatings were prepared by multi-arc plating technique as a function of N 2 pressure. The as-deposited coatings demonstrate a bct-Ti 2 N + fcc-TiN dual-phase structure below 1.2 Pa, and single-fcc structure at above 1.2 Pa. Single-fcc phase Ti-Mo-N coatings show considerable higher hardness and load-bearing capacity compared to pure TiN coating due to alloying effect of Mo. Transmission electron microscope (TEM) study unveil that GB plays the key role in the deformation behaviors. The Mo-doped TiN coatings exhibit enhanced plastic deformation ability of GBs, including substantial plastic flow and twinning, which retard intergranular cracking that is geometry necessary during GB glide and rotation. While the appearance of the bct -Ti(Mo) 2 N phase leads to stress concentration at bct-fcc interface during deformation because of the large lattice misfit, considerably lowering load-bearing capacity. In addition, Ti-Mo-N coatings have lower friction coefficient (COF) and wear rate than TiN coating in reciprocal tribology tests, which is attributed to the higher hardness and toughness, as well as tribochemistry-induced solid lubricant effect. • Mo doping results in substantial hardening-toughening effect. • GB plastic behaviors play the critical role. • Enhanced GB plasticity leads to high load-bearing capacity. • bct-fcc interfaces cause stress concentration and embrittlement.