For environmental reason, buildings increasingly install smart windows, which can dim incoming daylight based on active electrochromic devices (ECDs). In this work, multi-layered graphene (MLG) was investigated as an ECD window electrode, to minimize carbon dioxide (CO ) emissions by decreasing the electricity consumption for building space cooling and heating and as an alternative to the transparent conductor tin-doped indium oxide (ITO) in order to decrease dependence on it. Various MLG electrodes with different numbers of graphene layers were prepared with environmentally friendly poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) to produce ECD cells. Tests demonstrated the reproducibility and uniformity in optical performance, as well as the flexibility of the ECD fabrication. With the optimized MLG electrode, the ECD cells exhibited a very fast switching response for optical changes from transparent to dark states of a few hundred msec.