Through　regulating　the　pH　values,　a　series　of　iodo-argentate/cuprate　hybrids,　[Me3(4-TPT)]4[Ag6I18]　(1,　Me3(4-TPT)=N,N’,N’＇-trimethyl-2,4,6-tris(4-pyridyl)-1,3,5-triazine),　[Me3(4-TPT)][M5I8]　(M=Ag/2,　Cu/2a),　[Me3(3-TPT)][M5I8]　(Me3(3-TPT)=N,N’,N’＇-trimethyl-2,4,6-tris(3-pyridyl)-1,3,5-triazine,　M=Ag/3,　Cu/4),　which　exhibit　adjustable　structural　variations　with　different　dimensional　structures,　have　been　obtained　under　solvothermal　conditions.　They　are　directed　by　two　types　of　in　situ　N-alkylation　TPT-derivatives　(Me3(4-TPT)　for　1/2/2a　and　Me3(3-TPT)　for　3/4)　and　represent　the　isolated　units　(1),　1D　polymeric　chain　(4),　2D　layered　structures　(2/2a,　3)　based　on　diverse　metal　iodide　clusters.　These　compounds　possess　reducing　band　gaps　as　compared　with　the　bulk　β-AgI　and　CuI　and　belong　to　potential　semiconductor　materials.　Iodocuprates　feature　highly　efficient　photocatalytic　activity　in　the　sunlight-induced　degradation　of　organic　dyes.　The　detailed　study　on　the　possible　photocatalytic　mechanism,　including　radical　trapping　tests　and　theoretical　calculations,　reveals　that　the　N-alkylation　TPT　moieties　contribute　to　the　narrow　semiconducting　behavior　and　effectively　inhibit　the　recombination　of　photogenerated　electronhole　pairs,　which　result　in　an　excellent　visible-light-induced　photocatalytic　performance.　©　2019　Wiley-VCH　Verlag　GmbH&Co.