Photochromic diarylethene polymers (DPs) in which 1,2-bis(2-methylbenzo[b ]thiophene-3-yl)hexafluorocyclopentene (BTF6) were covalently grafted onto the polymer main chain as pendant photochromic units were newly synthesized and their photochromic properties were investigated using steady-state and picosecond timeresolved spectroscopies. Polysiloxanes substituted with BTF6 molecules were prepared by sol-gel process using a mixture of tetraethoxysilane (TEOS), a silylated BTF6, and an organically modified silane precursor in the presence of HCl. The polysiloxane film (DP1) prepared from $omega-methoxy$ poly(ethylene glycol) 3-(triethoxysilyl) propylcarbainate (MPGSC) as the silane precursor showed a much lower glass transition temperature than that (DP2) from heptadecafluorodecyltrimethoxysilane (HDFTMS). The ring-closure quantum yields of DP1 and DP2 were determined to be 0.20 and 0.02, respectively. Such a large difference in the quantum yield was attributed to the polymer matrix environment of the free inner volume.