To investigate solid-solution formation in the iron-doped silicate (zircon) system, different samples were prepared by the ceramic method with addition of LiF as a mineralizer. The results of X-ray powder diffraction (XRD), Fe-57 Mossbauer, and UV-visible spectroscopy showed that in the as-prepared samples, only a small fraction of iron, i.e., about 2.5 mol%, is hosted in the zircon structure as paramagnetic Fe 31 species, while the remaining Fe3+ cations form magnetic alpha-Fe2O3 particles that are trapped in the zircon matrix.