Abstract The surfactant assisted synthesis of disc-shaped WO3 powder and its photocatalytic performance in sunlight exposure is reported. UV–vis DRS, XRD and FESEM characterized the synthesized WO3. The synthesized powder exhibited a bandgap of ∼2.55eV with cubic lattice and high crystallinity. The photocatalytic activity of the synthesized WO3 was examined for the degradation of phenol, resorcinol, 2-chlorophenol and 2-nitrophenol in complete spectrum and visible segment of sunlight. The highly efficient degradation/mineralization of 2-chloro and 2-nitrophenol compared to that of phenol and resorcinol, under identical experimental conditions, suggested the regulatory role of substituents attached to the aromatic ring in degradation/mineralization process. The time-scale HPLC degradation profiles, identification of intermediates by GC-MS and removal of organic carbon during the course of reaction were utilized to approximate the possible route of degradation/mineralization of phenolic substrates. The measurement of the anions released during the photocatalytic process was used to identify the nature of the major oxidants (O2•−, OH•) and the possible interaction sites. A significant decrease in the photocatalytic activity of synthesized WO3, ∼50%, was observed in visible portion of sunlight however, a sustained activity was observed in the repeated exposures.