Viologen　bismuthate　halides　generally　show　photochromic　properties.　In　the　present　work,　phenylethyl　alcohol　was　introduced　into　chloro　bismuthates　in　the　hope　to　prepare　photochromic　crystalline　materials　and　finally　a　photochromic　inorganic-organic　hybrid,　(PeV)(3)(Bi2Cl9)(2)　(1),　based　on　an　in　situ　generated　PeV(2+)　cation　(PeV(2+)　=　phenethylviologen　=　N,N　＇-diphenethyl-4,4　＇-bipyridinium),　has　been　obtained,　whose　microstructure　contains　a　discrete　dimer　[Bi2Cl9](3-)　counterion　identified　by　single　crystal　X-ray　diffraction.　More　importantly,　1　exhibits　a　typical　photochromic　behavior,　which　can　be　mainly　attributed　to　the　reversible　inter-conversion　between　the　monocation　viologen　radical　[PeV](+center　dot)　and　the　viologen　dication　[PeV](2+).　[GRAPHICS]　.