This study tended to decipher the mechanism of photo degradation of azo dyes, which bond was favorable to be broken for application of wastewater decolorization. That is, from chemical structure perspective, the critical substituents to affect electron donor/acceptor for dye degradation would be identified in this research. The model reactive blacks (RB5), reactive blue 171 (RB171) and reactive red 198 (RR198) were degraded by graphene loaded TiO2, indicating how the electron withdrawing and releasing groups affect azo dye degradability. The byproducts and intermediate products were analyzed by ultraviolet-visible spectroscopy (UV-vis), gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC). Furthermore, the radicals involved in the reaction were found by electron paramagnetic resonance (ESR) to confirm the main oxidized species of hydroxyl radicals rather than the light generated positive holes. The finding revealed that the breakages of the bonds were due to the electron density changes around the bonds. This principle can be applicable not only for RB5 degradation, but also for reactive blue 171 (RB171), reactive red 198 (RR198) and some other textile dyes. (C) 2015 Elsevier B.V. All rights reserved.