Two　triphenylmethylphosphonium/haloplumbate　hybrids,　i.e.,　[(PPh3Me)(2)(Pb2I6)center　dot　CH3CN](n)　(1)　and　[(PPh3Me)(PbBr3)](n)　(2),　have　been　prepared,　in　which　the　(PbX3)(n)(n-)　nanochains　built　from　face-sharing　PbX6　octahedra　are　surrounded　by　organic　templates　to　assemble　the　core-shell　quantum　well.　Besides,　C-H　center　dot　center　dot　center　dot　pi　interactions　among　Ph3PMe+　cation　can　also　be　detected,　which　give　rise　to　the　2-D　organic　layer　of　1　and　1-D　chain　for　2.　The　good　water　stabilities　could　be　induced　by　the　strong　C-H　center　dot　center　dot　center　dot　pi　interactions,　which　can　deter　the　hydrolysis　reaction.　The　energy　band　gaps　of　this　work　mainly　derive　from　the　charge　transfer　of　organic　components,　but　their　luminescence　stems　from　the　inorganic　(PbX3)(n)(n-)　nanochains　with　co-existence　of　free　excitons　and　self-trapped　excitons.　At　temperature　lower　than　117　K,　strong　quantum　confinement　will　rule　out　the　free　excitons,　and　self-trapped　excitons　will　dominate,　resulting　in　red-shift　luminescence.　Moreover,　effective　and　repeatable　photocurrent　responses　can　be　found　in　these　hybrids.