In this work, the study of photocatalytic hydrogen production by RGO/ZnIn2S4 with simultaneous degradation of organic amines was carried out in the presence of organic amines in wastewater as the sacrificial agents. The effects of several factors, such as organic amine types, pH value, catalyst concentration, organic amine concentration, and sunlight source, on the photocatalytic activity of RGO/ZnIn2S4 for H2 production were investigated. At the same time, its performance of degrading organic amines during H2 production was also examined. The results showed that the order of H2 production activity of RGO/ZnIn2S4 in six organic amine solutions was N(CH2CH3)3 > N(HOCH2CH2)3 > N(CH3)3 > HO(CH2)2NH2 > C6H5-N2> CO(NH2)2, and the highest H2 production was in N(CH2CH3)3 (triethylamine) solution, being 1597 μmol·g-1·h-1, which is 2.6 times as high as that using the aqueous solution mixture of Na2S and Na2SO3 as the sacrificial agent. In addition, when the pH was 13, the catalyst concentration was 1.0 g·L-1, and the triethylamine concentration was 1.0 mol·L-1, the photocatalytic activity was the highest. Furthermore, the relationship between triethylamine concentration and H2 production was analyzed according to the theory of dynamics.