A structural investigation of a synthesized precursor in a silica glass matrix is performed. Silica soot samples are doped with the heterobimetallic precursor ErNb2(OPri)13 by using a conventional solution doping technique and heat treatments to different temperatures. The precursor has also been introduced into a silica fiber preform by using the modified chemical vapor deposition technique. Analyses are made by using ultraviolet–visible–near infrared absorption spectroscopy, scanning electron microscopy, energy dispersive spectroscopy and powder X-ray diffraction. It is concluded that an immiscible system of ErNbO4 crystallites and Nb2O5 is formed in the silica soot samples at high temperatures. Colloidal particles of ErNbO4 are also formed in the silica glass fiber preform showing interesting features.