We investigate the effect of Fe and Cr doping at Zn and V sites, respectively, on the electrical transport behavior of polycrystalline spinel ZnV2O4. The resistivity studies as a function of temperature reveal the presence of two different transport mechanisms: Arrhenius conduction (170–300 K) and Mott variable range hopping conduction (VRH) (80–170 K). The results also show that Fe doping at Zn sites has a pronounced effect on the electrical transport property together with the V–V distance, accompanied by a decreasing magnetic transition temperature, T N . Cr doping, on the other hand, shows a contrasting Arrhenius transport behavior with decreasing V–V distance as well as a decreasing T N . In the VRH transport regime, a systematic variation of the values of the Mott parameters due to the change in the localization length along the V–V chains is observed. Further, x-ray Photoelectron spectroscopy studies supporting the stabilization of the doped cation phases are presented in this paper.