A methodology for the analysis of the siting of Zn 2+ ions in extra-framework cationic sites of silicon-rich zeolite was developed and demonstrated on Zn-ferrierite samples (Si/Al 8.5, Zn/Al 0.04−0.33). This methodology is based on the FTIR spectroscopy of antisymmetric tetrahedral−octahedral−tetrahedral (T-O-T) vibrations of the zeolite framework perturbed by Zn 2+ ions, combined with a complementary approach based on Zn 2+ luminescence monitored by laser-induced timeresolved luminescence spectroscopy. Three vibration bands in the FTIR spectra of antisymmetric T-O-T vibrations of dehydrated zeolite reflect Zn 2+ ligation in three extra-framework cationic sites of ferrierite zeolite. The band at 935 cm −1 corresponds to Zn 2+ ions in the α-site of ferrierite, the band at 917 cm −1 correspondsto ions in β-site, and the band at 902 cm −1 correspondsto Zn 2+ ions in the γ-site. The extinction coefficient for quantitative analysis of Zn 2+ ions in cationic sites was estimated and exhibited the same value for Zn 2+ cations in all cationic sites, ε = 49.1 ± 3.8 cm•μmol −1 . In all Zn samples, Zn 2+ siting in the β-site prevails, while Zn 2+ ions in the γ-site are of low population or negligible. Time-resolved luminescence showed that bare Zn 2+ ions in the extra-framework cationic sites can be distinguished from Zn 2+ ions in ZnO by a decay time which is several magnitudes longer and a high sensitivity for quenching. The luminescence spectrum of Zn-ferrierites is composed of three bands at 545, 480, and 425 nm attributable to Zn 2+ ions in the α-, β-, and γ-site with luminescence coefficients (for semiquantitative analysis) ζ α = 10.1, ζ β = 9.4, and ζ γ = 8.8 mmol/g of Zn 2+ ions in the α-, β-, and γ-sites, respectively. The analysis of Zn ions in ferrierites showed that ZnH-ferrierites exclusively contain Zn 2+ ions in cationic sites. In the case of the ZnNa-FER sample with maximum Zn loading (Zn/Al 0.33), a small amount of Zn-oxo species can be formed.