In this work photodegradation rates and pathways of malachite green were studied under simulated and solar irradiation with the goal of assessing the potential of photolysis as a removal mechanism in real aquatic environment. Factors influencing the photodegradation process were investigated, including pH, humic acid, Fe2+, Ca2+, HCO3-, and NO3-, of which favorable conditions were optimized by the orthogonal array design under simulated sunlight irradiation in the presence of dissolved oxygen. The degradation processes of malachite green conformed to pseudo first-order kinetics and their degradation rate constants were between 0.0062 and 0.4012 h(-1). Under solar irradiation, the decolorization efficiency of most tests can reach almost 100%, and relatively thorough mineralization could be observed. Forty degradation products were detected by liquid chromatography-mass spectrometry, and thirteen small molecular products were identified by gas chromatography-mass spectrometry. Based on the analyses of the degradation products and calculation of the frontier electron density, the pathways were proposed: decomposition of conjugated structure, N-demethylation reactions, hydroxyl addition reactions, the removal of benzene ring, and the ring-opening reaction. This study has provided a reference, both for photodegradation of malachite green and future safety applications and predictions of decontamination of related triphenylmethane dyes under real conditions. (C) 2014 Elsevier B.V. All rights reserved.