Three　porous　heterovalent　cluster　organic　frameworks　Cu2(H2O)(Cu4I4)(INA)4·solvent　(1),　Cu2(H2O)2(Cu4I4)2(INA)4(DABCO)2·2DMA　(2)　and　[(Cu2)2(PVBA)8(Cu4I4)]·DMF　(3)　(HINA　=　isonicotinic　acid,　DABCO　=　1,4-diazabicyclo[2.2.2]octane,　HPVBA　=　4-(2-(4-pyridyl)ethenyl)　benzoic　acid,　DMF　=　N,N′-dimethylformamide,　DMA　=　N,N′-dimethylacetamide)　have　been　solvothermally　synthesized　and　structurally　characterized.　Crystal　structure　analyses　indicate　that　compounds　1　and　2　are　constructed　from　planar　four-connected　Cu2(CO2)4　secondary　building　units　(SBUs)　and　tetrahedral　four-connected　Cu4I4　SBUs,　while　compound　3　is　composed　of　octahedral　six-connected　Cu2(CO2)4　SBUs　and　tetrahedral　four-connected　Cu4I4　SBUs.　All　these　frameworks　possess　nano-sized　1-dimensional　channels.　Furthermore,　the　thermal　and　chemical　stabilities,　gas　adsorption　properties　and　iodine　adsorption/release　ability　of　compound　2　have　been　systematically　studied.　©　2020　The　Royal　Society　of　Chemistry.