The tribological behaviors of Ti-Ni51.5 at% alloy strengthened by finely dispersed Ni4Ti3 particles in reciprocating sliding against GCr15, Al2O3, and ZrO2 at room temperature were studied. Interestingly, the coefficient of friction (COF) suffered a sheer drop (from 0.9 to 0.2) when the aged alloy slid against GCr15 at a frequency of 20 Hz under a 20 N load without lubrication. However, severe-mild wear transition disappeared when a solutionized alloy was used. Moreover, the COF stabilized at a relatively high level when Al2O3 and ZrO2 were used as counterparts, although their wear mechanisms showed signs of oxidation. Scanning electron microscopy (SEM) and X-ray element mappings of the wear scars of the counterparts clearly indicate that the formation of well-distributed tribo-layer and material transfer between the ball and disk are pivotal to the severe-to-mild wear transition in the aged Ti-Ni51.5 at% alloy/GCr15 friction pair. The higher microhardness and superelasticity of the aged alloy significantly accelerate the material transfer from GCr15 to the disk, forming a glazed protective tribo-layer containing Fe-rich oxides.