Perovskite　hybrids　of　lead　organometal　halides,　most　notably　CH3NH3PbI3,　have　shown　extremely　promising　applications　in　the　field　of　optoelectronics,　because　of　their　remarkable　semiconducting　and　light-absorbing　properties.　However,　two　key　issues—the　toxicity　of　lead　and　the　poor　ambient　instabilities—have　restrained　their　further　commercialization.　Herein,　we　have　designed　a　new　stable　polar　lead-free　hybrid　material　by　utilizing　the　strategy　of　cation　substitution,　[(CH3)3N]3Bi2I9　(1),　which　adopts　the　0D　inorganic　perovskite-like　architecture　by　face-sharing　BiI6　octahedra.　It　is　interesting　that　1　displays　excellent　absorbing　properties　with　a　narrow　optical　band　gap　of　≈2.0　eV,　and　positive　temperature-dependent　conductivity　confirms　its　semiconducting　behaviors.　In　addition,　1　has　good　phase　stability　against　decomposition　under　ambient　conditions,　much　superior　to　that　of　CH3NH3PbI3.　This　work　suggests　the　potential　of　1　as　a　lead-free　semiconducting　absorber　with　high　phase　stability　for　photoelectric　applications.　©　2017　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim