The　search　for　new　heterometallic　metal　pseudohalides　will　be　significant　for　the　development　of　novel　functional　materials.　In　this　work,　a　new　silver/cadmium　heterometallic　thiocyanate　templated　by　benzyl　viologen　has　been　synthesized　and　structurally　determined,　i.e.,　{(BV)[Ag2Cd(SCN)6]}n (BV2+　=　benzyl　viologen).　The　interesting　1-D　double　chain　[Ag2Cd(SCN)6]n2n−　was　constructed　from　the　CdN6　octahedron　and　Ag2SCN6　dimers　via　μ2-SCN　and　μ3-S,S　N　SCN　bridge,　in　which　the　Ag···Ag　interaction　can　be　found.　Inter-molecular　C-H···S/N　hydrogen　bonds　between　BV2+　cations　and　[Ag2Cd(SCN)6]n2n−　chains　contribute　to　the　formation　of　a　stable　3-D　network.　The　short　S···N　distance　implies　the　strong　charge　transfer　(CT)　interactions　between　the　electron-rich　silver/cadmium　thiocyanate　donor　and　BV2+　acceptor.　This　hybrid　can　exhibit　a　photo-generated　current　performance　with　an　intensity　of　1.75　×　10−8　A.　Interestingly,　this　hybrid　can　present　good　photocatalytic　degradation　performance　on　rhodamine　B　in　artificial　seawater　with　a　degradation　ratio　of　86.5%　in　240　min.　This　work　provides　a　new　catalyst　way　for　the　organic　dye-type　ocean　pollutant　treatments.　©　2024　by　the　authors.