The re-melting coating of NiCrBSi+TiN metal-ceramic powders sprayed on the surface of Ti6Al4V alloy was performed by CO2 laser. By means of scan electron microscopy (SEM) and X-ray diffraction (XRD), microstructure of the coating was investigated and microhardness was measured. The effect of TiN on microstructure is discussed. The experimental results show that the phase of coating are composed of (Cr-Ni-Fe), TiN, NiB, Cr2Ti, Ti2Ni et al.. The TiN particles are dissolved into [Ti] and [N] during laser heating, intermetallic compound Cr2Ti and Ti2Ni result from some of the [Ti] combining with Ni, Cr, and TiN, TiN0.3, TiN0.9 precipitated during cooling in differ position. Thickness of the diffusion layer is approximately 5～6 μm existing between the dilution zone (DZ) and the heat-affected zone (HAZ), concentration gradient of Ni is distinctness in the diffusion layer.