This study reports the effect of vanadium on the crystal structure and electrical and electrochemical properties of La0.6-xVxSr0.4MnO3-delta (X = 0.005-0.1) perovskite-based cathode materials in solid oxide fuel cells. Crystal structure, morphology, and porosity of prepared cathode materials are characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. Using XPS analysis it was established that the La3+ cation is exchanged by the V4+/5+ cation in the perovskite structure. This ion replacement improves the ionic conductivity and catalytic activity for oxygen reduction reaction in the perovskite structure, presumably due to the smaller size of the V4+/5+ cation than the La3+ ion. Oxygen partial pressure-related polarization experiments suggest that the adsorption-desorption process and the reactions controlled by the atomic oxygen diffusion process followed by charge transfer are the cathode reaction rate-limiting steps.