Storage of solar radiation is currently accomplished by coupling two separate devices, one that captures and converts the energy into an electrical impulse (a photovoltaic cell) and another that stores this electrical output (a battery or a supercapacitor electrochemical cell). This configuration however has several challenges that stem from a complex coupled-device architecture and multiple interfaces through which charge transfer has to occur. As such presented here is a scheme whereby solar energy capture and storage have been coupled using a single bi-functional material. Two electroactive semiconductors BiVO4 (n-type) and Co3O4 (p-type) have been separately evaluated for their energy storage capability in the presence and absence of visible radiation. Each of these have the capability to function as a light harvester and also they have faradaic capability. An unprecedented aspect has been observed in that upon photo-illumination of either of these semiconductors, in situ charge carriers being generated play a pivotal role in perturbing the electroactivity of the redox species such that the majority charge carriers, viz. electrons in BiVO4 and holes in Co3O4, influence the redox response in a disproportionate manner. More importantly, there is an enhancement of ca. 30% in the discharge capacity of BiVO4 in the presence of light and this directly provides a unique route to augment charge storage during illumination.