Zhang et al. reported the sp 2 -hybridized carbon atoms dominant in its aromatic rings, with oxygen heteroatoms doped porous carbon as supercapacitor electrode materials . In this study, the porous carbon materials were prepared using a biphenylene-bridged hybrid porous solid (BS) as the precursor. The BS samples were heated at different temperatures under Ar atmosphere, and treated with 40 wt% HF solution to obtain the porous carbon materials and were abbreviated as BS-700, BS-800, BS-850, BS-900, BS-950, BS-1000, BS-1050, and BS-1100, BP-2000. The SBET of BS materials was determined from BET analysis, which showed 609. for BS, BS-700, BS-800, BS-850, BS-900, BS-950, BS-1000, BS-1050, and BS-1100, respectively. The XPS studies showed the presence of C and O atoms in BS and BS-1000, in which the content of hydroxyl groups was much higher in BS-1000 than that in BS, signifying the enhancement in the wettability of the carbon surface. The electrochemical performance of the BS materials for supercapacitors were performed in 2 M H2SO4 or 6 M KOH electrolyte solution, and carried out in a 3-electrode system, as well as in two-electrode system using glassy carbon electrode as working electrode. Among all the fabricated electrodes, the BS-1000 electrode showed the largest specific capacitance of 256 F g -1 at 1 A g -1 with the energy density of 5.75 W h Kg -1 , and the power density of 100 W Kg -1 in 2 M H2SO4, which is attributed to its large SBET, high oxygen content, and hierarchical micro-mesopores that facilitated quick mass transfer and smooth diffusion of electrolytes on the electrode. For the current density of 20 A g -1 , the specific capacitances were decreased by of the initial values for BS-700, BS-800, BS-850, BS-900, BS-950, BS-1000, BS-1050, and BS-1100, respectively. Further, the symmetric coin cell electrodes were fabricated using titanium foils, and BS-1000 as current collectors, and active materials, respectively, which could illuminate a light emitting diode (LED) by a stack of coil cell, and displayed the specific capacitance within 198.4 -145.8 F g -1 at a current density in the range of 1-10 A g -1 .