The flexible Li-O battery is suitable to satisfy the requirements of a self-powered energy system, thanks to environmental friendliness, low cost, and high theoretical energy density. Herein, a flexible porous bifunctional electrode with both electrocatalytic and photocatalytic activity was synthesized and introduced as a cathode to assemble a high-performance Li-O battery that achieved an overpotential of 0.19 V by charging with the aid of solar energy. As a proof-of-concept application, a flexible Li-O battery was constructed and integrated with a solar cell via a scalable encapsulate method to fabricate a flexible self-powered energy system with excellent flexibility and mechanical stability. Moreover, by exploring the evolution of the electrode morphology and discharge products (Li O ), the charging process of the Li-O battery powered by solar energy and solar cell was demonstrated.