A photovoltachromic device includes a photoelectrode, a counter electrode electrically connected to the photoelectrode, and an electrolyte layer disposed between the photoelectrode and the counter electrode. The photoelectrode includes a first transparent electrode, an electron-transport layer disposed on the first transparent electrode, and a sensitizing layer disposed on the electron-transport layer. The counter electrode includes a second transparent electrode and an electrochromic layer disposed on the second transparent electrode. The second transparent electrode contacts both of the electrolyte layer and the electrochromic layer thereby accelerating the response times for coloring and bleaching the photovoltachromic device.