A systematic investigation of the IR and Raman spectra of pure and Al-, B-, Ti- and Fe-substituted silicalites in the SiO stretching region (1500–700 cm^–1) is presented. As well as the characteristic stretching modes of the skeleton, silicalites containing hydroxylated nests show also broad bands at ca. 960 cm^–1(IR) and at ca. 976 cm^–1(Raman), associated with O₃Si—OH group modes, with prevailing Si—OH stretching character. The replacement of Si with heavier elements (like Ti or Fe) causes the appearance of new IR- and Raman-active modes (i) at 960 cm^–1(IR and Raman) and at 1127 cm^–1(Raman) in Ti silicalite; (ii) at 1015 cm^–1(IR) and at 1020 cm^–1(Raman) in Fe silicalite. Neither the Raman nor the IR spectra of the skeletal modes are substantially modified by the introduction of Al (ZSM5). The presence of boron induces the appearance in the IR spectra of a complex absorption at 1380 cm^–1 and at 960–930 cm^–1, which corresponds to the absorptions at 1417 and 976 cm^–1 in the Raman spectra. The assignment of the absorptions associated with heteroatoms and hydroxylated nests is discussed in detail.