Thermochemotherapy has shown a synergistic anti-cancer efficiency and can enhance the therapeutic effect of simple chemotherapy. The photothermal conversion characteristics of carriers are vital in thermo-chemotherapy. Therefore, hollow mesoporous carbon (HMC) with excellent heating efficiency and a large specific surface area was used to ensure the high loading capacity. Next, approximately 4 nm spherical gold nanoparticles (NPs) were employed as gatekeepers of the tunnels of HMC by Au-S bonds, which have the same size as HMC mesopores. Additionally, the gold NPs could avoid the premature release of the drug and enhance the photothermal properties of the delivery system. The surface of the carriers was modified with polyethylene glycol (PEG) to increase the biocompatibility and dispersity of doxorubicin (DOX) loaded DOX/HMC-Au@PEG. DOX release was markedly accelerated in the presence of glutathione (GSH) and near-infrared (NIR), indicating that the system had redox and NIR dual-triggered drug release characteristics. Cytotoxicity experiments proved that combined therapy induced the highest cell killing level. Additionally, the combination index (CI) of DOX/HMC-Au@PEG was 0.452, indicating the synergistic effect of chemotherapy and photo-thermal therapy (PTT). In vivo antitumor experiments were also carried out and showed the same trend. In general, the results of this study indicated that DOX/HMC-Au@PEG has great potential in dual-triggered drug delivery and thermochemotherapy.