The purpose of the present study was to experimentally assess the synergistic effects of wear and corrosion on NiTi alloy in comparison with Ti-6Al-4V alloy, the most extensively used titanium alloy in biomedical applications. Both alloys were processed by an additive manufacturing laser beam directed energy deposition (LB-DED) technique, namely laser engineered net shaping (LENS), and analyzed via tribocorrosion tests by using the ball-on-plate configuration. The tests were carried out in phosphate buffered saline solution at 37 °C under open circuit potential (OCP) to simulate the body environment and temperature. The synergistic effect of wear and corrosion was found to result in an improved wear resistance in both materials. It was also observed that, for the process parameters used, the LB-DED NiTi alloy exhibits a lower tendency to corrosion as compared to the LB-DED Ti-6Al-4V alloy. It is expected that, during the service life as an implant, the NiTi alloy is less susceptible to the metallic ions release when compared with the Ti-6Al-4V alloy.