A series of CaIn2S4-reduced graphene oxide (RGO) nanocomposites with different RGO contents were fabricated using a facile hydrothermal approach. During the hydrothermal process, the reduction of graphene oxide to RGO, in situ deposition of synthesized CaIn2S4 nanoparticles on RGO nanosheets and formation of chemical-bonding CaIn2S4-RGO nanocomposites were performed simultaneously. Under visible light irradiation, the as-prepared CaIn2S4-RGO nanocomposites showed enhanced photocatalytic performance for rhodamine B degradation and phenol oxidation. The sample with 5 wt % RGO hybridized CaIn2S4 exhibited the highest photocatalytic activity. The enhancement of photocatalytic performance may be related to the increased adsorption/reaction sites, positive shift of the valence band potential, and high separation efficiency of photogenerated charge carriers due to the electronic interaction between CaIn2S4 and RGO. We hope that this work can not only provide an in-depth study on the photocatalytic mechanism of RGO-enhanced activity, but also provide some insights for fabricating efficient and stable RGO-based photocatalysts in the potential applications of purifying polluted water resources.