Two　semiconductive　inorganic-organic　hybrid　coordination　polymers　constructed　from　metal　iodide　clusters　and　naphthalene　diimide　semiconductive　components,　[Cu2I2(DPNDI)]n　(1)　and　[PbI2(DPNDI)]n　(2)　(DPNDI　=　N,N′-di-(4-pyridyl)-1,4,5,8-naphthalene　diimide),　have　been　synthesized　and　characterized.　Although　possessing　similar　2D　heterostructures,　hybrids　1-2　exhibited　different　photo-induced　electron-transfer　properties.　Due　to　the　higher　HOMO　energy　level　of　the　[Cu2I2]n　chain　than　that　of　the　[PbI2]n　cluster,　only　hybrid　1　can　easily　undergo　intramolecular　electron　transfer　to　form　a　long-lived　charge　separated　state,　which　may　be　applied　in　artificial　photosynthesis.　©　The　Royal　Society　of　Chemistry　2016.