In this study, we used the facile solvent evaporation method to achieve the inorganic-organic hybrid crystals of [triethylpropylammonium][PbI3], which have been characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and differential scanning calorimetry as well as single-crystal X-ray structure analysis. The hybrid solid-crystallizes in the monoclinic-space,group P2(1)/c at room temperature and is composed of one-dimensional [PbI3](infinity) chains, where the neighboring PbI6 coordinatio-n octahedra connect together via the face-sharing mode and the organic cations fall in spaceS between [PbI3](infinity) chains. The hybrid exhibits a dielectric phase transition with a critical temperature of ca. 432 K, dielectric relaxation at frequencies below 10(7) Hz, and single-ion conducting behavior, the conductivity of which increases rapidly from 9.43 X 10(-10) S cm(-1) at 383 K to 4.47 X 10(-5) S cm(-1) at 473 K. The variable-temperature single-crystal and powder X-ray diffraction analyses revealed that the dielectric phase transition is related to the disorder-to-order transformation of cations in the lattice. The electric modulus and impedance spectral analyses further disclosed that the dielectric relaxation arises from the ionic displacement polarization and molecular dipole orientation of cations. The single-ion conductance is due to the migration of cations that fall in the spaces of rigid inorganic [PbI3](infinity) chains. The phase transition gives rise to this hybrid showing switchable ion-conducting nature around the critical temperature of the phase transition. Besides the fascinating functionalities mentioned above, the hybrid also exhibits a thermochromic luminescence feature originating from the electron transition between the valence and conduction bands of the inorganic [PbI3](infinity) chain.