Electroactive microorganisms (EAMs) can act as pseudocapacitor to store energy and discharge electrons on need, while electromethanogens acting as receptor are able to utilize electrons, protons and carbon dioxide for methanization. However, external energy is required to overcome thermodynamical barriers for electromethanogenesis. Herein, electro-driving power by solar light was established to accelerate conversion of waste organics to bioenergy. The intermittent power supply modes were elucidated for favourable performances (e.g., current density, methane production rate, energy recovery efficiencies and economic evaluation), compared with the control driven by continuous applied voltage. It was found that natural intermittent solar-powered mode was more beneficial for microorganisms involved in electron transfer and energy recovery than manual sharp on-off mode. Electrochemistry analysis unrevealed that a higher redox current and lower resistance were exhibited under the solar-powered mode. A high charge storage capacity and electron mobility were found through cytochrome c content and live cells ratio in the solar-power assisted bioreactor. The intermittent power driving modes can regulate electron transfer proteins with capacitive storage behavior in biomass, which helps to understand the responses of functional communities on the stress of intermittent electric field. These findings indicate a promising perspective of microbial biotechnology driven by solar power to boost bioenergy recovery from waste/wastewater.