In this paper, a study on the removal of imitated polystyrene (PS) microplastics in water was carried out based on the adsorption capacity of three-dimensional reduced graphene oxide (3D RGO). Scanning electron microscopy and X-ray diffractometry characterization showed that the freeze-dried 3D RGO formed a distinct porous spatial structure. Different experimental parameters, such as pH, ion concentration (C0), contact time (t), and temperature (T), were studied to investigate the PS microplastic adsorption performance of 3D RGO. The adsorption mechanism was mainly attributed to the strong π–π interaction between the carbon ring of 3D RGO and the benzene ring of PS microplastics. Sorption kinetic and isothermal data were obtained by the well-fitted Langmuir adsorption isotherm model and pseudo-second-order kinetic model. Furthermore, the result of thermodynamic analysis showed that the adsorption of PS microplastics was a spontaneous endothermic process. Under the optimal conditions of pH = 6, C0 = 600 mg/L, t = 120 min, and T = 26 °C, the maximum adsorption capacity of the prepared 3D RGO on PS microplastics was 617.28 mg/g. Furthermore, this method exhibited good feasibility in tap water and lake water.