Multifunctional cancer treatments based on gas therapy combined with other cancer treatments have gained tremendous attention and hold great promise in biomedical applications. In this study, a carbon monoxide-releasing nanoplatform combined with near-infrared (NIR) laser-triggered photothermal therapy (PTT) was constructed. The nanoplatform was composed of manganese pentacarbonyl bromide (MnCO)-loaded g-carbon nitride/polypyrrole (CNPpy) nanomaterials (MnCO@CNPpy). MnCO can be triggered to produce CO under HO conditions. Upon exogenous NIR light stimulation and tumor microenvironment-overexpressed HO, MnCO@CNPpy exhibited excellent CO generation performance and photothermal effect. The generation of CO induced intracellular oxidative stress and caused cell apoptosis. Additionally, photoacoustic (PA) imaging was performed to track the delivery and accumulation of the nanomaterial in tumor sites because of the great photothermal conversion of CNPpy. The presented MnCO@CNPpy nanoplatform displayed desirable PTT and CO therapy in the inhibition of tumor growth and may provide a promising strategy for multifunctional antitumor synergistic treatments.