This study investigates the degradation of organophosphorus pesticides coupled with hydrogen (H2) production using titanium dioxide modified with fluoride and platinum (F−/TiO2@Pt). In the presence of dicrotophos (300 μM) under anoxic conditions, F−/TiO2@Pt achieved complete degradation and produced 17.87 μmol of H2 after 4 h. In contrast, only 42.4 μM, 92.4 μM, and 251.5 μM of dicrotophos were degraded using bare TiO2, F−/TiO2, and TiO2@Pt, respectively, with significantly lower or negligible H2 production (i.e., 6.60 μmol with TiO2@Pt and negligible amounts with bare TiO2 and F−/TiO2). The markedly enhanced degradation of dicrotophos and H2 generation by the dual surface modification with F− and Pt, compared to single-component modifications, is attributed to the synergistic action of F− and Pt in suppressing charge recombination and promoting electron transfer to H+. Beyond dicrotophos, F−/TiO2@Pt also exhibited superior degradation efficiency and H2 production compared to TiO2@Pt in the presence of various organophosphorus pesticides, including dichlorvos, trichlorfon, acephate, ethoprophos, methacrifos, and fenamiphos. Furthermore, F−/TiO2@Pt outperformed TiO2@Pt under all tested experimental conditions, including variations in F− concentration, catalyst dosage, Pt loading, and pH, except at pH 11.0. This study demonstrates an effective surface modification strategy for dual-function photocatalysis targeting organophosphorus pesticide degradation and H2 production.