AbstractPhotothermal therapy (PTT), as an important noninvasive and effective tumor treatment method, has been extensively developed into a powerful cancer therapeutic technique. Nevertheless, the low photothermal conversion efficiency and the limited tissue penetration of typical photothermal therapeutic agents in the first near‐infrared (NIR‐I) region (700–950 nm) are still the major barriers for further clinical application. Here, we proposed an organic/inorganic dual‐PTT agent of synergistic property driven by polydopamine‐modified black‐titanium dioxide (b‐TiO2@PDA) with excellent photoconversion efficiency in the second NIR (NIR‐II) region (1000–1500 nm). More specifically, the b‐TiO2treated with sodium borohydride produced excessive oxygen vacancies resulting in oxygen vacancy band that narrowed the b‐TiO2band gap, and the small band gap led to NIR‐II region wavelength (1064 nm) absorbance. Furthermore, the combination of defect energy level trapping carrier recombination heat generation and conjugate heat generation mechanism, significantly improved the photothermal performance of the PTT agent based on b‐TiO2. The photothermal properties characterization indicated that the proposed dual‐PTT agent possesses excellent photothermal performance and ultra‐high photoconversion efficiency of 64.9% under 1064 nm laser irradiation, which can completely kill esophageal squamous cells. Meanwhile, Gd2O3nanoparticles, an excellent magnetic resonance imaging (MRI) agent, were introduced into the nanosystem with similar dotted core–shell structure to enable the nanosystem achieve real‐time MRI‐monitored cancer therapeutic performance. We believe that this integrated nanotherapeutic system can not only solve the application of PTT in the NIR‐II region, but also provide certain theoretical guidance for the clinical diagnosis and treatment of esophageal cancer.