In this work, we apply polarized Raman spectroscopy for study of internal vibrations of the 3-cyanopyridinium cation in the halide post-perovskite (3cp)PbBr3 (3cp = 3-CN-C5H5NH+). For a single cation, the vibrational frequencies and intensities of the Raman signal were calculated using the density functional theory. Selection rules were established for vibrations of cations in the crystal. These rules together with modeling results were used to identify the internal vibrations of the cation in the Raman spectrum of the crystal. Narrow and isolated internal vibrations of cations could be used as spectators of the crystalline environment.