Cu2-xS nanocrystals (NCs), characterized by low cost, low toxicity, high stability and high photothermal conversion efficiency, provide promising platforms as photothermal agents. Herein, a novel twostep synthesis has been developed for Cu7S4 nanocrystals with hollow structure using the as-prepared copper nanoparticles as starting a solid precursor followed by hot-injection of sulfide source.The Cu7S4 NCs exhibit intense absorption band at Near-infrared (NIR) wavelengths due to localized surface plasmon resonance (LSPR) mode, which can effectively convert 980 nm-laser energy into heat.Moreover, the localized high temperature created by Cu7S4 NCs under NIR irradiation could result in efficient photothermal ablation (PTA) of cancer cells in vivo, demonstrating a novel and promising photothermal nanomaterials.