To solve the problems of high nitriding temperature and long nitriding time with conventional plasma nitriding technologies, a kind of low-temperature plasma oxy-nitriding technology containing two-stage processes with different ratios of N to O was developed on a TC4 alloy in this paper. A thicker permeation coating can be obtained with this new technology compared to conventional plasma nitriding technology. The reason for this is that the oxygen introduction in the first two-hour oxy-nitriding step can break the continuous TiN layer, which facilitates the quick and deep diffusion of the solution-strengthening elements of O and N into the titanium alloy. Moreover, an inter-connected porous structure was formed under a compact compound layer, which acts as a buffer layer to absorb the external wear force. Therefore, the resultant coating showed the lowest COF values during the initial wear state, and almost no debris and cracks were detected after the wear test. For the treated samples with low hardness and no porous structure, fatigue cracks can easily form on the surface, and bulk peeling-offcan occur during the wear course.