A round-the-clock Ag/BiO2−x/Bi2O2.75 energy storage catalyst with the unique electron-hole storage mechanism is prepared by natural photo-deposition method. Ag is directional deposited on the surface of BiO2−x due to the Z-scheme mechanism, and electrons and holes are severally stored in Ag and Bi2O2.75. The recombination of electron-hole pairs is efficiently suppressed owing to the formation of Schottky junction, and the capacitance nature of Ag, leading to that the concentrations of the stored electrons and holes are markedly increased from 24.94 and 0.0042 μmol·g−1 to 86.55 and 0.0481 μmol·g−1. Hence, Ag/BiO2−x/Bi2O2.75 shows the boosted and long-lasting dark catalytic activity for organic pollutants mineralization, meanwhile possessing appealing structural stability, recyclability and repairability. Furthermore, the generation of the reactive oxygen species is promoted and NO oxidation pathway is changed due to the light-induced surface plasmon resonance effect of the stored electrons and holes and the resultant near-field enhancement effect, resulting in the significantly enhanced full-spectrum photocatalytic performance for antibiotic degradation and NO deep oxidation. This work may open up new horizons for the design and preparation of high-active round-the-clock catalytic materials.