The growth dynamics of hard Cr-V composite surface layer on AISI D3 cold work steel surface was investigated, where the coating was fabricated by Thermo-reactive deposition at 1000 °C. The heating durations critically contributes to the microstructure evolution as well as the coating adhesive strength and mechanical properties. Surface and interface structural changes were observed by Scanning Electron Microscopy, Energy Dispersive X-ray spectroscopy, and X-ray diffraction. The results well show, the growth of Cr-V composite layer depends on the coating process duration, the thickness of obtained coatings ranged from 5.0 to 11.8 μm. The obtained coating demonstrates the multilayered structure consisting of the carbide located at the outmost layer and diffusion layer of Fe-Cr solid solution. The coating demonstrates desirable adhesive strength and toughness. A possible growing model of formation process for the Cr-V composite surface layer was proposed.