Propylene oxide (PO) is a key industrial chemical, often produced by epoxidizing propylene with H<sub>2</sub>O<sub>2</sub> over titanium silicalite-1. However, current H<sub>2</sub>O<sub>2</sub> production via the anthraquinone process relies on fossil-derived hydrogen, leading to substantial CO<sub>2</sub> emissions. Sustainable PO synthesis requires green H<sub>2</sub>O<sub>2</sub> production. Here, we present a fully unassisted, solar- and bias-free system that generates H<sub>2</sub>O<sub>2</sub>. This platform enables modular, eco-friendly on-site PO synthesis by coupling formaldehyde oxidation with two-electron O<sub>2</sub> reduction under alkaline conditions. Efficient propylene epoxidation under these conditions is achieved using titanium silicalite-1 modified by introducing dinuclear titanium sites with Ti-O-Ti bonds, as revealed by density functional theory and instrumental analyses. The unassisted H<sub>2</sub>O<sub>2</sub> production system is integrated with the modified titanium silicalite-1 to realize continuous PO production (1657 μmol<sub>PO</sub> cm<sup>-2</sup> over 24 h), without electric or solar energy input. This unassisted PO production method can thus be energy-independent, offering a sustainable alternative to conventional processes.