The combined properties of reduced graphene oxide/polypyrrole (rGO/Ppy) have drawn a lot of interest in composite electrodes for supercapacitors. In this work, chemical bath deposition (CBD) method was used to develop rGO/Ppy composite thin films. The CBD method enables the synthesis of self-supported electrode materials, optimizing the physicochemical characteristics and promoting efficient charge transfer of electrodes for energy storage systems. The characterization of rGO/Ppy thin films by X-ray diffraction, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy revealed the presence of amorphous Ppy with a spherical morphology on rGO layers. The rGO/Ppy thin films exhibited remarkable electrochemical properties, obtaining 987 F g−1 specific capacitance at scan rate of 5 mV s−1 and retaining 87% electrochemical stability after 3,000 cycles. Moreover, an aqueous asymmetric supercapacitor device (rGO/Ppy//H2SO4//WO3) demonstrated a 61 F g−1 specific capacitance and 11 Wh kg−1 specific energy at 0.474 kW kg−1. This study reveals an easy method for enhancing Ppy charge storage capacity and cyclic stability through composition of rGO for supercapacitor applications.