Two triphenylmethylphosphonium/haloplumbate hybrids, i.e., [(PPh₃Me)₂(Pb₂I₆)∙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···π interactions among Ph₃PMe⁺ cations 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···π 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.