To study the formation mechanism and stability of the phase in the interface of tungsten carbide particles reinforced iron matrix composites, the composites were fabricated by spark plasma sintering (SPS) technique and combined with first-principles calculation. It was found that Fe3W3C compound was stable from the perspective of both thermodynamics and mechanical properties based on our calculations. Interfacial reaction product of tungsten carbide particles reinforced iron matrix composites was M6C. Experimental results indicated that the samples prepared by SPS did not appear interfacial reaction zone, while, interfacial reaction zone appeared for the remelted samples. With the increasing remelting temperature, the width of the interface reaction zone increased because the mutual diffusion occurred at the interface between tungsten carbide particles and matrix. Its formation mechanism was 3Fe + 3/2W2C → Fe3W3C + 1/2C. Our research might provide a theoretical guidance in controlling the interface of tungsten carbide particles reinforced iron matrix composites.