The photocatalytic degradation of rhodamine B (RhB) over NaBiO3 under visible light irradiation was investigated in this study. RhB (20 mg/L.) was almost completely decolorized in 30 min in given conditions. It was found that catalyst heating temperature significantly influenced the photocatalytic activity of the catalyst in which crystal water may played an important role, and the original sample exhibited higher activity than the heated samples did. To scrutinize the mechanistic details of the dye photodegradation, several critical analytical methods including UV-vis spectroscopy, HPLC, LC/MS/MS, and GUMS were utilized to monitor the temporal course of the reaction. All N-deethylation intermediates and several small molecular products were separated and identified. The yield distinctness between two isomer intermediates (DR and EER) was considered to be correlated with the changes in the electron density of the dye molecule. Then two possible competitive photodegradation pathways of RhB over NaBiO3 were proposed: Chromophore cleavage and N-deethylation. Yet, cleavage of dye chromophore structure predominated over the N-deethylation.