Experimental results indicate that vanadium affects the solidification process in high chromium iron. Vanadium is distributed between eutectic M7C3 carbide and the matrix, but its content in carbide is considerably higher. Also, this element forms vanadium carbide. TEM observation reveals that vanadium carbide present in examined Fe-Cr-C-V alloys is being of M6C5 type. DTA analysis found that with increasing vanadium content in tested alloys, liquidus temperature is decreasing, while eutectic temperature is increasing, i.e. the solidification temperature interval reduces. The narrowing of the solidification temperature interval and the formation of larger amount of vanadium carbides, as a result of the increase in the vanadium content of the alloy, will favour the appearance of a finer structure. In addition, the phases volume fraction will change, i.e. the primary -phase fraction will decrease and the amount of M7C3 carbide will increase.