An all-solid-state electrochromic window (SEW) of prussian blue and electrodeposited WO3 film with poly(vinyl chloride) PVC gel electrolyte with high conductivity (2 mS/cm) at room temperature has been fabricated. The SEW has been found to be excellent for electrochromism and memory characteristics. W 4f core level of WO3 film as a function of the injected charge has been investigated using X-ray photoelectron spectroscopy (XPS). W 4f peaks become broader after coloration.