Osteosarcoma, the most common primary malignant bone tumor in adolescents, faces treatment challenges due to metastasis and chemoresistance. This study developed a novel Au@Rh core-shell nanoparticle system functionalized with indocyanine green (ICG) to overcome hypoxia-limited photodynamic therapy (PDT). Au@Rh nanoparticles were synthesized via wet chemistry, characterized by UV-Vis spectroscopy, TEM, and cyclic voltammetry (CV). The system exhibited core-shell morphology, defined crystalline planes, photothermal conversion and electrocatalytic activity. The Au@Rh nanoparticles (109 nm total size, 90 nm Au core, 15 nm Rh shell) demonstrated dual functionality: the gold core provided photothermal conversion (7 °C temperature increase under NIR irradiation), while the rhodium shell exhibited pH-independent electrocatalytic activity for H₂O₂ decomposition, generating oxygen to alleviate tumor hypoxia. Crucially, the system showed excellent biocompatibility, with no significant cytotoxicity in both osteosarcoma (HOS) and normal osteoblast (hFOB) cells after 48-hour exposure. When activated by NIR irradiation (808 nm, 16.6 J/cm²), the complete Au@Rh-ICG system achieved selective 67% cytotoxicity in HOS cells versus only 30% in hFOB cells, demonstrating targeted therapeutic efficacy. These results position Au@Rh-ICG as a promising theranostic platform for osteosarcoma treatment, combining enhanced PDT with photothermal therapy while addressing tumor hypoxia.