To study the effect of Zn substitution on structural magnetic properties and hyperfine interactions of barium hexaferrite, BaFe12-x Zn (x) O-19 (0.0aexae0.3) hexaferrites were synthesized via sol-gel auto-combustion technique. Rietveld analysis of XRD powder patterns confirmed the formation of single-phase hexaferrites for all products. Due to the larger ionic size of Zn2+ as compared with Fe3+, while x increases, the lattice constant parameters increase to a small degree. Nanoplate morphology of the products is presented by SEM analyses. It was observed that both saturation magnetization and coercivity decrease in almost the same manner with zinc concentration for all substitutions. Cation distribution calculations showed that Zn2+ occupies 12k, 4 f (2), 4 f (1), and 2b sites and at the same time pushes Fe3+ ions towards 2a and 12 k (1) sites. From(57)Fe Mossbauer spectroscopy data, the variation in line width, isomer shift, quadrupole splitting, and hyperfine magnetic field values on Zn2+ substitution have been determined.