Abstract Cost‐effective, stable, and highly efficient heterogeneous catalyst is the key challenge for wastewater treatment based on Fenton‐like advanced oxidation processes. Perovskite oxides offer new opportunities because of their versatile compositions and flexible physiochemical properties. Herein, a new strategy is proposed that is different from the frequently used alien‐metal doping, to tune surface properties of perovskite oxides by nanocompositing perovskite with inert oxide, resulting in improved activity and stability for catalytic oxidation. By in situ modification of LaFeO 3 with inert La 2 O 3 oxide through one‐pot synthesis, several important surface properties such as surface defects, H 2 O 2 adsorption capacity, Fe 2+ concentration, and charge‐transfer rate were improved, as well as resistance against iron leaching. In performance evaluation, among the various materials, La 1.15 FeO 3 (L 1.15 FO) composite shows the highest Fenton activity (0.0402 min −1 ) for activating H 2 O 2 to oxidize methyl orange, 2.5 times that of the pristine LaFeO 3 . Notably, in situ electron paramagnetic resonance analysis and radical scavenging tests unveil a faster generation of singlet oxygen as the dominant reactive species over L 1.15 FO, consequently a novel non‐radical activation mechanism is proposed. Such improved performance is assigned to the strong coupling effect between the nanosized LaFeO 3 and La 2 O 3 in the hybrids, which fine‐tune the surface properties of LaFeO 3 perovskite as superior Fenton catalysts.