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Raman and infrared reflection spectra in the backbone deformations and lattice modes range (10−1000 cm-1) of EB/ES-I and EB/ES-II polyanilines are discussed and compared with those of an oligomer (BQBBa) and of the constitutive bricks of the polyaniline skeleton:  diphenylamine (BB), N,N‘-diphenyl-1,4-phenylenediamine (BBB), and N,N‘-diphenyl-1,4-phenylenediimine (BQB). Short-range structure, scaling motif, and disorder are discussed. Emphasis is given to the relationship between hybridization, short-range structure, disorder, and optical properties. Ring, CH deformations, and librational/translational modes appear very sensitive to the static and dynamic disorder. Results show that vibrational spectroscopy allows to distinguish the two classes of polyaniline (ES-I and ES-II), whatever the inserted anion. The sketch of a continuous change of angle between the rigid virtual N−ring−N bond is proposed to describe the static orientational disorder.