Polyethylenimine (PEI) mediated reduced graphene oxide (rGO) based paper is presented as novel material for flexible supercapacitor. It is demonstrated that the pristine rGO sheets store energy by physical adsorption of charged species; whereas PEI mediated rGO enhances the electrochemical reactivity by increasing the number of adsorption edges for charge species that also induces the redox reaction during electrochemical performance. The presented symmetric supercapacitor rGO-PEI//rGO-PEI possesses high areal capacitance of 180 mF/cm2 at the charge/discharge current density of 1 mA/cm2. In addition, the supercapacitor demonstrates very good capacitive retention of 94.17% of its initial capacitance after 5000 cycles.