This work developed novel transparent nanocomposite film with thermochromic and hydrophobic properties fabricated by electrospinning and hot-pressing approach. The homogeneous composite nanofibers mats were obtained via co-electrospinning the organic polymer polymethylmethacrylate (PMMA) and inorganic VO2 (M) nanoparticles. The VO2 (M) nanoparticles with average diameter of 30 nm were distributed in the electrospun nanofibers and isolated from air simultaneously, which was beneficial for antioxidation of the VO2 (M). Additionally, the mechanical property of the nanocomposite films with different stacked layers was always improved significantly via hot-pressing treatment. Moreover, the thermochromic property of the film showed the solar modulation ability Delta T-sol of 7.31% and the luminous transmittance of 29.6% at 550 nm. Thus, the study offered a new notion for the energy-saving material, and it could be a good promising substitute of smart glass.