We report effect of V substitution in Cr-sites of Fe2CrAl on electronic properties in the present article. The electronic structure calculations of Fe2Cr1-xVxAl alloys clearly exhibit a significant effect of decreasing number of valence electron on density of state (DOS) for majority-spin state as well as magnetic properties of half-metallic ferromagnetic Fe2CrAl Heusler alloy, but retains high degree of spin polarization across this series (100% for x= 0.75). © 2012 American Institute of Physics.