The nanocomposites comprising of reduced graphene oxide (rGO) and polyaniline (PANI) were synthesized by facile insitu single step chemical methods, with glacial acetic acid (AA) and methane sulphonic acid (MSA) as dopants for PANI. The rGO/PANI nanocomposites synthesized with the similar weight percentages of constituents exhibited better electrochemical performance in the presence of MSA than in the presence of AA, in the real two-electrode supercapacitor cell system. The nanocomposite of weight percentages of rGO-6.7%, and PANI-93.33% (GP93MSA), with MSA as dopant exhibited a remarkable feature of increase in energy storage when the number of cycles was increased. It exhibited a maximum enhancement of 237.44% in its energy storage performance, after 13600 cycles as compared to the performance before the onset of cyclic test. The high performances obtained with GP93MSA include high specific capacitance of 512.82 F g−1, specific capacity of 615.38 C g−1, energy density of 102.56 W h kg−1 and a power density of 1.8954 kW kg−1 at 1 A g−1. The energy density of the supercapacitor with GP93MSA as the electrode material, is of the same order as that of Li-ion batteries. Also, GP93MSA showcased good cyclic stability up to 23000 cycles.