Using a CO2 laser, a process of cladding Ni-base composite coating on Ti6Al4V with pre-placed B4C and NiCoCrAlY was studied. A good metallurgical bonding coating without cracks and pores was obtained in reasonable ratios of components and low energy laser process. Morphology and microstructure of the coating were analyzed with OM, XRD, SEM and EDS. It is certain that there was a reaction between B4C and Ti during in-situ producing TiB2 and TiC. The Ni-base composite coating is strengthened with TiB2 and TiC reinforcement phases. Vickers Hardness Tester measured that the average microhardness of the coating is HV1200 and it is 3.5 times of the Ti6Al4V substrate. The high hard coating containing several reinforcement phases greatly enhances wear resistance of titanium alloy.