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　(Bi　2　Cl　9　)　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　[Bi　2　Cl　9　]　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]　+•　and　the　viologen　dication　[PeV]　2+　.　(Figure　presented.).　©　2019,　©　2019　Informa　UK　Limited,　trading　as　Taylor　&　Francis　Group.