The microstructure, mechanical and micro/nano-tribological properties of the 60NiTi film annealed at different temperature were investigated. The results reveal that annealing as-deposited 60NiTi film at 300, 375, and 600 °C for 1 h leads to structural relaxation, partial crystallization and full crystallization, respectively. Compared with the structurally relaxed structure, the partially crystallized structure exhibits increased hardness but decreased elastic modulus. This is because that the elastic modulus is reduced by Voigt model while the hardness is improved by composite effect. Due to the highest hardness and ratio of hardness to elastic modulus (H/E), the partially crystallized 60NiTi film has the lowest penetration depth and residual depth (i.e., groove depth). Besides, the results also reveal that ductile plowing is the dominant wear mechanism for all the annealed 60NiTi films. Under the condition of the ductile plowing, coefficient of friction and wear resistance are related to penetration depth and residual depth, respectively. Therefore, the partially crystallized 60NiTi film shows the best tribological performance at the micro/nano-scale. The current work not only highlights the important roles of hardness and H/E in improving the micro/nano-tribological properties but also concludes an efficient and simple method for simultaneously increasing hardness and H/E.