Global warming and the global energy crisis are two major challenges humanity is currently confronting that are pressuring the scientific community to find efficient, low cost and environmentally sustainable solutions. Within this context, hydrogen has emerged as a clean and efficient energy carrier promising to replace the environmentally hazardous fossil fuels. The present study, of relevance to the water splitting domain, concerns the synthesis of two novel hybrid structures, based on perovskite materials functionalized with polyvinylpyrrolidone (PVP). The water electrolysis catalytic activity of these new materials was evaluated in a strongly alkaline medium. Perovskite-based modified electrodes were manufactured through four different procedures. The samples displayed electrocatalytic activity for the O2 evolution reaction and the most active electrode was the one obtained by drop-casting a mixture of LaMnO3:Ag/PVP, Carbon Black and Nafion on graphite support. The study is aimed at and succeeds in increasing the scientific database concerning the role of perovskite oxides in the water splitting field.