In this work, the Micro-properties such as stability, mechanical parameter and bonding structures of (Nb,M)C carbides (M ¼ V, Mo, W and Cr) were calculated. And the misfit and interfacial combination between (Nb,M)C carbides and Fe matrix were investigated by first principles calculation. The precipitation behavior of (Nb,V)C carbides were studied. The element V distribution of the carbide in the coatings were analyzed by experiments. The calculation results show that, in the (Nb,M)C carbides, the lattice constant and formation energy of Nb0.75V0.25C carbide are the smallest, and its hardness and brittleness are the largest. According to bonding analysis, Nb-C covalent bonds are the main factor for its high hardness in Nb0.75V0.25C carbide. The combination between carbide and Fe matrix is improved from the results of misfit and adhesion work. Based on the diagrams of the hardfacing alloys with different V contents, the fraction of MC carbides is increased with increase of V contents, and VC carbide can precipitate when V content is high enough. It indicates that element V can be introduced into NbC carbide from the chemical elements analysis experiments.