Phototherapy, including photothermal and photodynamic therapy, has gained extensive attention in the tumor treatment field recently, while synergistic therapy can significantly improve curative effects. However, a complicated photo-responsive nanosystem, different excitation wavelengths, and low tissue depth hindered its actual application. Herein, single near-infrared responsive PEGylated defective MoO2 nanocrystals were fabricated by a green hydrothermal method. The photothermal and photodynamic performances of the samples were presented in detail under a safe power of 1064 nm (NIR-II, 1.0 W cm-2). Interestingly, the photodynamic properties were prompted by the localized surface plasmon resonance (LSPR) photothermal effect obviously, and the collaborative enhancement mechanism was explored in depth. Subsequently, the in vitro cytotoxicity was evaluated on the 4T1 cancer cells under NIR-II irradiation. This work may provide guidance for the facile fabrication of TMOs for NIR-II responsive and enhanced dual-modal phototherapy.