Additive manufacturing of NiTi alloys has garnered significant attention in the field of medical implants due to their precision and high-quality molding, and their prominent mechanical properties. However, NiTi alloy as an implant material still faces critical challenges. Herein, the silane coating is applied on the additive-manufactured NiTi alloy, and a multifunctional GO/Ti3C2 heterojunction is introduced to enhance its anticorrosion, wear resistance, biocompatibility, and antibacterial properties. The GO/Ti3C2 heterojunction enhances the corrosion resistance and stability of the silane coating through the “labyrinth effect,” and improves the wear resistance of NiTi alloy by establishing a lubricating film. Additionally, GO/Ti3C2 demonstrated excellent biocompatibility and efficient photothermal performance. In vitro experiments show that this coating considerably promoted the growth and proliferation of MC3T3-E1 cells, with a cell viability of 128%. Moreover, after 10 min of Near-infrared irradiation (NIR), the antibacterial efficiency of this coating against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) reached 98% and 96%, respectively. Furthermore, the silane/GO/Ti3C2 coating effectively encouraged immune cells to shift toward M2 macrophage polarization in vivo implantation experiment. Overall, the multifunctional silane coating with GO/Ti3C2 heterojunctions has the potential to promote the application of additive manufacturing NiTi alloys in the medical field.