The　organic-inorganic　donor-acceptor　(D-A)　hybrid　hetemstructures,　an　emerging　class　of　hybrid　complexes　containing　semiconductive　organic　dyes　and　inorganic　pigments　at　a　molecular　level,　have　displayed　extraordinary　optoelectronic　properties　and　applications.　Herein,　we　demonstrated　that　the　combination　of　dipyridylnaphthalene　diimide　tecton　(DPNDI)　with　CuI　(or　AgOOCF3)　resulted　in　two　isostructural　D-A　hybrid　heterostructures　based　on　1D　[Cu8I14](6)　or　[Ag8I14](6)　polyanions　surrounded　by　an　interwoven　network　of　in　situ　N-methylated　DPNDI　cations.　Due　to　the　compact　contact　between　these　two　semiconductive　components　by　the　charge-assisted　anion-ic　and　C-H　center　dot　center　dot　center　dot　I　hydrogen-bonding　interactions,　the　obtained　hybrid　materials　not　only　display　high　chemical　stability　but　also　exhibit　high　efficiency　and　moderate　stability　in　the　photoreduction　of　Cr　(VI)　upon　visible　light　irradiation.　The　influences　of　various　experimental　conditions　on　the　photocatalytic　reactions　including　pH　value　and　hole　scavenger　have　been　investigated.　In　addition,　the　possible　mechanism　studied　shows　that　photogenerated　electrons　are　the　main　active　substances　in　the　photoreduction　of　Cr(VI).　This　study　suggests　that　constructing　D-A　hybrids　heterostructures　by　two　functional　components　with　noncovalent　interactions　are　promising　for　developing　the　hybrids　used　in　the　reduction　of　Cr(VI)　in　the　future.