Mo-doped tungsten bronzes were hydrothermally synthesized at 80 °C. Samples transformed from hexagonal to monoclinic structure with Mo-content increase. 1.5% Mo-doped samples show the best near-infrared shielding performance. High Mo-doping weakens localized surface plasmon resonance (LSPR) absorption and thus NIR shielding performance. Small polaron absorption seems to be less affected by Mo-doping.