Thermochromic W- and Mo-doped VO 2 (M) with a various doped contents were successfully synthesized using peroxovanadium (V) complexes as the vanadium precursor and green solvent (ethanol) as the reducing agent by a facile hydrothermal approach and subsequent calcination for the first time. The samples were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductive coupled plasma emission spectrometer (ICP), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). The results revealed that W or Mo atoms were successfully doped into the crystal lattice of VO 2 matrix, and the as-prepared W- and Mo-doped VO 2 (M) had a belt-like morphology. The phase transition temperature of doped VO 2 (M) could be simply tuned by changing the doping concentration of W or Mo atoms. The variable-temperature infrared spectra disclosed that the doped VO 2 (M) had outstanding thermochromic characters and optical switching properties.