Series of new MxMO3/ZnO (M=K, Rb, NH4) nanocomposites were successfully prepared by simple two-steps method in a mild condition. The as-prepared MxWO3/ZnO composite films showed nice UV light blocking, VIS light transmittance and NIR light shielding properties. Furthermore, the optical properties of the composites could be tuned by adjusting the MxWO3 content and film thickness. Particularly, the RbxWO3/ZnO with small amounts of RbxWO3 contents exhibited the promising optical properties and also excellent thermal stability. From the practical application viewpoint, the simulated experiment found that the simulated house decorated with sample film as smart window presented nice NIR light induced heat insulation. for energy saving, and the RbxWO3/ZnO decorated one was even better than that of ITO. In addition, both the powder and film samples displayed high continuously toxic NO gas decomposing ability under the IN light irradiation. The mechanisms for the multifunctionality of the samples were related to the polaron transition, localized surface plasma resonance (LSPR) and suitable band gaps. Therefore, the new MxWO3/ZnO composites and relevant films not only showed promising harmful UV light absorption, high VIS light brightness, excellent NIR light induced heat insulation, but also nice toxic NO gas photodecomposition property, indicating their brilliant prospect in both of energy saving and environmental cleanup. (C) 2016 Elsevier B.V. All rights reserved.