Structural studies of iron vanadate glasses were carried out using differential thermal analysis, infrared (IR) and Mössbauer spectroscopy. Glasses with cross-lining density higher than the vitreous VO were obtained by introducing FeO in the VO matrix. Mössbauer spectra are consistent with an interpretation in which iron ions exist as Fe with tetrahedral coordination in the glass compositions. IR spectra indicate that Fe ions occupy substitutional positions in all glass compositions, without affecting the V=O bond vibration.