A self-charging supercapacitor is constructed through simple integration of the energy storage and photo exited materials at the photo electrode. The large band gap of NiO//Fe3O4 heterostructure generates photo electron at the photo electrode and store the charges through redox mechanism at the counter electrode. Sulfanilic acid azocromotrop/reduced graphene oxide layer at the photo electrode trapped the photo generated hole and store the charge by forming double layer. The solar supercapacitor device is charged within 400 s up to 0.5 V and exhibited a high specific capacitance of ~908 F/g against 1.5 A/g load. The solar illuminated supercapacitor shows a high energy and power density of 33.4 Wh/kg and 385 W/kg along with a very low relaxation time of ~15 ms ensuring the utility of the self charging device in the various field of energy storage and optoelectronic application.