A printable photovoltaic electrochromic device is provided. The device includes a transparent substrate, at least one thin-film solar cell on the transparent substrate, at least one single polarity electrochromic (EC) thin film, wherein the single polarity electrochromic thin film includes a single polarity electrochromic material and a polyelectrolyte. The thin-film solar cell at least includes an anode layer, a cathode layer, and a photoelectric conversion layer between the anode layer and cathode layer, wherein a portion of the anode layer or a portion of the cathode layer is exposed from the thin-film solar cell. The single polarity electrochromic thin film covers and contacts with both the cathode layer and the anode layer.