Diarylethenes having thiophene unit show low oxidation potential to afford polymer film by electrochemical polymerization. The thickness of the polymer deposit on the electrode was conveniently controlled by the number of the potential cycles. The polymeric films showed reversible photocurrent generation property, by the alternative irradiation with a light. The photo-electrode prepared from a mixture of diarylethene and an electroactive monomer or nanoparticles showed much increased photocurrent generation with faster response An all solid type photocell structure was prepared to show high open circuit voltage (Voc) of 0.79 V under a simulated sunlight (100mW/cm²).