In this work, we have demonstrated a prompt anodic electrochemical exfoliation of graphite into graphene sheets (GS) in aqueous media. For the synthesis of GS, a constant potential of +10 V has been applied between two identical graphite sheets in 0.1 M aqueous ammonium sulfate. The exfoliated GS were characterized via standard analytical tools such as Fourier transform infra red spectroscopy (FT-IR), X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy with energy dispersive spectrum (FE-SEM with EDS). Further, the electrochemical performance of GS coated Ni foam (GS/Ni foam) was assessed by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) techniques in 2 M KOH. The quasi-rectangular shaped voltammograms and charge-discharge curves in a three-electrode system evidenced the double-layer capacitance of GS and GS/Ni foam which exhibited maximum specific capacitance of 84.8 and 40. 8 F/g at 2 mV/s, and 0.1 A/g of current density, respectively. Moreover, the symmetric two-electrode performance of GS/Ni foam was also examined, which showed good energy density (3.03 Wh/kg) and power density (562.5 W/kg). This study proves that the anodically exfoliated GS can act as a good symmetric supercapacitor in KOH.