Abstract: In this work, Bi(OH)SO4 · H2O, a novel photocatalyst was prepared by a facile method. The sample was characterized by XRD, XPS, SEM, Mott-Schottky curve and ESR. The band gap of Bi(OH)SO4 · H2O is about 4.64 eV, and its CB and VB are estimated at –0.5 and 4.14 eV, respectively. Degradation of RhB and PhOH under UV light irradiation illustrates that the sample has good UV activity. The results of ESR spectra and tapping experiments indicate that the main active species in the photocatalytic reaction process are hydroxyl radicals, superoxide radicals and holes. A possible mechanism of catalytic degradation of organic pollutants was proposed. This semiconductor has a positive valence band and high oxidation capacity theoretically and it may have broad application in synthesizing highly efficient photocatalysts through doping other elements or creating heterojunctions.