A process of laser cladding of NiCrBSi+2%B4C powder on Ti–6Al–4V substrate to form a coating was carried out, a good coating without cracks and pores was obtained in the process. The microstructure and component of the coating were examined using SEM and EPMA. The interface between the coating and the substrate was metallurgical, The microstructure of NiCrBSi+2%B4C cladding layer consisted of the Ni-based matrix, and the uniformly dispersed reinforcement phases of TiB2, TiC, etc. The microhardness of the coating was measured using a Vickers hardness tester. The average microhardness of the composite coating was HV1200 HV1400, and it was three times higher than that of Ti-6Al-4V substrate.