Organic–inorganic　hybrid　perovskites,　with　the　formula　ABX3　(A=organic　cation,　B=metal　cation,　and　X=halide;　for　example,　CH3NH3PbI3),　have　diverse　and　intriguing　physical　properties,　such　as　semiconduction,　phase　transitions,　and　optical　properties.　Herein,　a　new　ABX3-type　semiconducting　perovskite-like　hybrid,　(hexamethyleneimine)PbBr3　(1),　consisting　of　one-dimensional　inorganic　frameworks　and　cyclic　organic　cations,　is　reported.　Notably,　the　inorganic　moiety　of　1　adopts　a　perovskite-like　architecture　and　forms　infinite　columns　composed　of　face-sharing　PbBr6　octahedra.　Strikingly,　the　organic　cation　exhibits　a　highly　flexible　molecular　configuration,　which　triggers　an　above-room-temperature　phase　transition,　at　Tc=338.8　K;　this　is　confirmed　by　differential　scanning　calorimetry　(DSC),　specific　heat　capacity　(Cp),　and　dielectric　measurements.　Further　structural　analysis　reveals　that　the　phase　transition　originates　from　the　molecular　configurational　distortion　of　the　organic　cations　coupled　with　small-angle　reorientation　of　the　PbBr6　octahedra　inside　the　inorganic　components.　Moreover,　temperature-dependent　conductivity　and　UV/Vis　absorption　measurements　reveal　that　1　also　displays　semiconducting　behavior　below　Tc.　It　is　believed　that　this　work　will　pave　a　potential　way　to　design　multifeatured　perovskite　hybrids　by　utilizing　cyclic　organic　amines.　©　2018　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim