Amorphous polymers are heavily utilized materials in selective laser sintering (SLS) due to their good dimensional accuracy. However, sintered parts of amorphous polymers cannot be used as functional parts owing to their poor forming performance, including their low relative densities and tensile strength. Therefore, post-processing methods are employed to enhance the mechanical properties of amorphous polymers SLS parts without damaging their relatively high dimensional accuracy. In this study, the forming process of selective laser sintering (SLS) and post-processing on polystyrene (PS) was investigated. The orthogonal experiment was designed to obtain the optimal combination of process parameters. The effect of a single process parameter and the laser volumetric energy density (LVED) on dimension accuracy and warpage of the sintered parts were also discussed. In addition, a three-dimensional (3D) thermal model was developed to analyze the temperature fields of single-layer SLS parts and PS powder sintering mechanism. Then, infiltrating with epoxy resin was employed to enhance the mechanical properties of the PS parts. Good resin-infiltrated formulation was obtained based on the mechanical property tests and fractured surface analysis. This research provides guidance for SLS process and post-processing technology in polymers.