A new diarylethene compound with donor and acceptor substituent was synthesized from 2,3-bis(2-methylbenzo[b]thiophene-3-yl)hexafluorocyclopentene (BTF) over 5 steps. The donor-acceptor structured BTF compound (TBTFE) showed spectral change to a longer wavelength through photochromism with a high cyclization quantum yield (0.56). The 3,4-ethylenedioxythiophene (T) and carboethoxy (E) groups directly connected to BTF unit promoted electrical change accompanied with the photoisomerization of the BTF unit. Photo-induced electrical switching was achieved from a photocell containing TBTFE doped polymer film, which showed reversible and stable current change over repeated cycles by the alternative UV/Vis irradiation, as estimated by the I-V plot.