Hypoxia at bone defect hinders mitochondrial OXPHOS, which is critical factor contributing to delayed or failed bone repair. How to restore OXPHOS through controlled oxygen supply is crucial for promoting bone repair. This study employs metal coordination and a W/O/W strategy to fabricate dual-network microsphere scaffolds encapsulating oxygen-releasing nanocapsules (AAMs@PC-O2), wherein NIR-triggered photothermal modulation of gas solubility enables spatiotemporally controlled oxygen release, thereby augmenting mitochondrial electron transport and oxidative phosphorylation in BMSCs to facilitate bone regeneration. Experimental results reveal that by optimizing the compositional ratio of oxygen-releasing nanocapsules and modulating the NIR irradiation duration, oxygen concentration can be precisely adjusted within the range of 0-12 mg/L. Furthermore, the scaffold enables timely oxygen replenishment following 24 h' hypoxia in BMSCs, rescuing cellular fate, mitigating hypoxia-induced apoptosis, and augmenting oxidative phosphorylation, thereby driving osteogenic differentiation and advancing bone regeneration.