To investigate the effects of substituent groups on the reductive degradation of azo dyes by zerovalent iron, Orange I, Orange II and Methyl Orange were selected as the model azo dyes with different substituent groups. The results showed that Orange I, Orange II and Methyl Orange could be effectively reduced by Fe(0), and the degradation of Orange I and Orange II could be described by the first-order kinetic model, while the degradation of Methyl Orange could be described by the zeroth-order kinetic model. The initial degradation rate followed the order as Orange I>Orange II>Methyl Orange under the same experimental conditions owing to the substituent effects. The degradation kinetic constants of Orange I and Orange II increased with the increase in the Fe(0) dosage, and with the decrease in the initial pH value and their initial concentration, while that of Methyl Orange increased with the decrease in the initial pH value, and with the increase in the Fe(0) dosage and their initial concentration. The results of high-performance liquid chromatography (HPLC)-mass spectra (MS) showed that sulfanilic acid was the same intermediate, while the second intermediate was 1-amino-4-naphthol for Orange I, 1-amino-2-naphthol for Orange II, and p-dimethylaminoaniline for Methyl Orange. It was suggested that the larger conjugated pi system of naphthalene rings of Orange I and Orange II for the delocalization of the nonbonding electron pairs of substituents and nitrogen in the azo bond might be favorable for the degradation of Orange I and Orange II, compared with the structure of Methyl Orange. The higher degradation rate of Orange I might be ascribed to its effective electron delocalization and favorable position effects, compared with Orange II. It should be concluded that the reductive degradation of azo dyes by zerovalent iron strongly depends on the effect of substituent groups.