A mathematical model of kinetics of carbide layer formed on the surface of steel in fused system was set up with the theory of non-stable diffusion mass transfer and regular solution sub-lattice. This model was analyzed and testified by the experiments in which the VC layers were formed on four kinds of steels as steel 45, 4Cr5Mo-SiV1, T10, and Crl2MoV immersed in the V2O5-Na2O-B2O5 fused system with the reducing agent of silicon. The results showed that there was a good agreement between the model and the experimental results; the growth speed of carbide layer depended on the factors of carbon activity in substrate, treatment temperature, kinds of carbides and its structure