The perovskite LaNiO3 was prepared by the sol-gel method. Electrodes of LaNiO3/Ni-PVC were obtained by painting a conductive Ni-PVC composite substrate with a suspension of the LaNiO3 powder in an ethanol-tetrahydrofuran mixture. They were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and energy dispersive spectroscopy (EDS). The study of the electrochemical response of this composite was performed in alkaline solutions by cyclic voltammetry, open circuit potential and by voltammetric charges. The state of the surface and the contribution of the Ni-PVC substrate in the electrochemical behavior of LaNiO3 were studied for the same electrode after prolonged repetitive potential cycling and oxygen evolution.