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Electrochromic devices are fabricated by using polyaniline (PANI) doped with poly(styrene sulfonic acid) (PSS) as coloring electrodes, poly(ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT-PSS) as complementary electrodes, and hybrid polymer electrolytes as gel electrolytes. The device based on LiClO4-based electrolyte (weight ratio of PMMA:PC:LiClO4 = 0.7:1.1:0.3) shows the highest optical contrast and coloration efficiency (333 cm2/C) after 1200 cycles in these devices, and the color changes from pale yellow (−0.5 V) to dark blue (+2.5 V). The spectroelectrochemical and electrochromic switching properties of electrochromic devices are investigated, the maximum optical contrast (Δ T%) of electrochromic device for ITO|PANI-PSS|PMMA-PC-LiClO4-SiO2|PEDOT-PSS|ITO are 31.5% at 640 nm, and electrochromic device based on LiClO4-based electrolyte with SiO2 shows faster response time than that based on LiClO4-based electrolyte without SiO2. [ABSTRACT FROM AUTHOR]