The NiTi-based intermetallic compound coating is in-situ synthesized on the surface of Ti-6Al-4V (TC4) substrate by the laser melting deposition (LMP) technique. The microstructure characteristics, microhardness and electrochemical corrosion resistance of this coating are investigated. The research results show that, this coating is mainly composed of the intermetallic compounds as NiTi, Ni3Ti, NiTi2, Ni4Ti3 and so on. The microhardness of this coating is up to 800 HV, which is about 1.3 times higher than that of the TC4 substrate. Inhomogeneous passive films are formed on the surface of the coating and there also exist many pittings, and thus there is a slight decrease in corrosion resistance of this coating compared with that of the TC4 substrate.