Abstract Tumor photodynamic therapy (PDT) relies on intratumoral free radicals, while the limited oxygen source and the depletion of tissue oxygen may exacerbate the hypoxia. As the treatment progresses, there will eventually be a problem of insufficient free radicals. Here, it is found that Au@CeO 2 nano‐rods (Au@Ce NRs), assembled by gold nano‐rods (Au NRs) and ceria nanoparticles (CeO 2 NPs), can efficaciously absorb near‐infrared light (NIR) to promote the release of oxygen and free radicals. Au@Ce NRs exhibit a higher proportion of Ce 3+ (Ce 2 O 3 ) after oxygen release, while Ce 3+ is subsequently oxidized to Ce 4+ (CeO 2 ) by trace H 2 O 2 . Interestingly, Au@Ce NRs re‐oxidized by trace H 2 O 2 can re‐release oxygen and free radicals again upon NIR treatment, achieving oxygenation/oxygen evolution, similar to charging/discharging. This loop maximizes the conversion of limited oxygen source into highly cytotoxic free radicals. As a result, when B16‐F10 cells are treated by NIR/Au@Ce NRs, more tumor cells undergo apoptosis, consistent with the higher level of free radicals. Importantly, NIR/Au@Ce NRs successfully suppresses tumor growth and promotes the generation of epidermal collagen fibers in the transplanted tumor model. Therefore, the rod‐shaped Au@Ce NRs provide an ideal platform for maximizing the utilization of intratumoral oxygen sources and improving the treatment of melanoma.