Synthesis of hybrid materials based on sulfonated polystyrene (SPS) and graphene (G) have been done. Polystyrene has sulfonated using homogeneous method with sulfonating agent trimethylsilyl chlorosulfonic (TMSCS). Graphene has derived from coal tailings that have been carbonized 400°C and pyrolysis 800°C. Sulfonation degree were obtained 125%, FTIR spectrum showed that a symmetric vibration sulfonate groupe at region 1310-1200 cm-1. Preparation of hybrid materials by mixing sulfonated polystyrene and graphene in solvent dimethyl formamide followed by step slowly evaporating the solvent at 45°C. Thermal properties have studied using TGA and DSC, electrical properties, conductivity and capacitance were measured using Impedance Analyzer at room temperature. From the measurements were obtained conductivity (σ) and capacitance (ε) maximum 13.94 mS/m and 188.32 nF/m respectively.