MoO3/V2O5 hybrid nanobilayers are successfully prepared by the sol–gel method with a spin- coating technique followed by heat -treatment at 350 °C in order to achieve a good crystallinity. The composition, morphology, and microstructure of the nanobilayers are characterized by a scanning electron microscope (SEM) and X-ray diffractometer (XRD) that revealed the a grain size of around 20–30 nm, and belonging to the monoclinic phase. The samples show good reversibility in the cyclic voltammetry studies and exhibit an excellent response to the visible transmittance. The electrochromic (EC) window displayed an optical transmittance changes (ΔT) of 22.65% and 31.4% at 550 and 700 nm, respectively, with the rapid response time of about 8.2 s for coloration and 6.3 s for bleaching. The advantages, such as large optical transmittance changes, rapid electrochromism control speed, and excellent cycle durability, demonstrated in the electrochromic cell proves the potential application of MoO3/V2O5 hybrid nanobilayers in electrochromic devices.