Direct hydroxylation of benzene towards phenol with high conversion and selectivity remains a great challenge. We report herein an efficient La2CuO4 perovskite catalyst for one‐step oxidation of benzene using hydrogen peroxide under mild conditions. The catalyst was characterized using XRD, TEM, XPS, TG‐DTA, and other advanced techniques. The one‐pot hydroxylation reaction carried out at 60 °C under optimum reaction conditions in the presence of catalytic material shows benzene to phenol transformation with 51% conversion with >99% selectivity with 65 percent peroxide efficiency, respectively. The influence of reaction conditions such as temperature, amount of oxidant, reaction time and mode of addition of the oxidant was crucial in selectivity optimization.