Geometry optimizations and followed frequency calculations were performed for PbI (PbI+, PbI, and PbI−), PbI2 (PbI2+, PbI2, and PbI2−), PbI3 (PbI3+, PbI3, and PbI3−), PbI4 (PbI4, PbI4−, and PbI42−), PbI5 (PbI5, PbI5−, PbI52−, and PbI53−), and PbI6 (PbI6−, PbI62−, PbI63−, and PbI64−) at the CCSD(T) level with aug-cc-pVDZ pseudopotentials and valence basis sets. Both PbI6− and PbI64− are unstable while both PbI62− and PbI63− are stable. All the optimized equilibrium structures can be described well with the single reference method such as DFT. The PbI bond length becomes larger while the PbI stretching frequencies become smaller as the structural unit has more electrons (such as from PbI4, PbI4−, to PbI42−). The unpaired electron is located on the Pb atom for PbI and PbI2− but is located on the I atoms for PbI2+, PbI3, PbI4−, PbI52−, and PbI63−. Harmonic vibrational frequencies plus adiabatic ionization potentials and electron affinities are reported.