The efficient removal of organic pollutants using singlet oxygen (1O2) represents a pivotal advancement in environmental purification. Despite its potential, the controlled generation of 1O2 remains a challenging endeavor. In this study, we present a novel approach whereby methyl/methylene are utilized to modulate the production of 1O2 by tungsten trioxide (WO3), thereby enhancing the photocatalytic degradation of persistent pollutants through deep oxidation. Employing a dodecyltrimethylammonium bromide (DTAB)-assisted hydrothermal synthesis, we successfully fabricated WO3 capable of generating 1O2. This modified WO3 demonstrates superior performance in the photocatalytic degradation of chloroquine phosphate by facilitating the rapid separation of photo-generated electron-hole pairs, thereby accelerating the degradation process. Furthermore, WO3 augmented with 1O2 exhibits enhanced efficacy in decomposing other challenging organic contaminants, compared to its untreated counterpart. Our findings not only contribute to the advancement of photocatalytic design principles centered on 1O2 but also underscore the critical role of controlled 1O2 production in the effective eradication of pollutants.