By utilizing in situ-formed MCP ligands (HMCP+ = 1-methyl-4-(carboxyl)pyridinium) as decoration agents, two new iodoplumbate hybrids, namely, [Pb(MCP)(2)I]PbI3 (1) and Cs-2[Pb(MCP)(4)]Pb3I10 (2), have been solvothermally prepared and structurally characterized. Compound 1 features the typical one-dimensional (1D) [PbI3](n)(n-) anions, while compound 2 exhibits two-dimensional (2D) [Pb3I10](n)(4n-) slabs perforated with large parallelogram-shaped windows. The intriguing structural characteristic of compounds 1 and 2 is that they contain unique chain-like cations of [Pb(MCP)(2)I](+) and [Pb(MCP)(4)](n)(2+), respectively. Interestingly, upon alternate visible-light and full spectrum light irradiation, compounds 1 and 2 show stable and rapid photoelectric switching properties, whose photocurrent densities are comparable or larger than those of many metal halide hybrids. Additionally, their optical properties, Hirshfeld surface analyses, X-ray photo-electron spectra, as well as the theoretical band structures and density of states have also been studied.