Organic-inorganic　hybrid　perovskites,　with　the　formula　ABX(3)　(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　ABX(3)-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　T-c=338.8K;　this　is　confirmed　by　differential　scanning　calorimetry　(DSC),　specific　heat　capacity　(C-p),　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　T-c.　It　is　believed　that　this　work　will　pave　a　potential　way　to　design　multifeatured　perovskite　hybrids　by　utilizing　cyclic　organic　amines.