To further elucidate the nature of the valence state of V ions in vanadate glasses,magnetic susceptibility measurements in the temperature range of 5 to 300 K have been performed on a series of vanadium–strontium–borate (V2O5+SrO+B2O3) oxide glasses with V2O5 concentrations greater than 50 mol %. The magnetic susceptibility for these oxide glasses is found to consist of a temperature-independentparamagnetic contribution arising from V2O5 and a Curie–Weiss temperature-dependent contribution associated with magnetic V4+ ions being present in concentrations between 2% and 10% of the total V concentration. The negative Curie–Weiss temperatures in the range of 0 to −2.8 K indicate a weak antiferromagneticinteraction between the V4+ ions. These results are consistent with a glass network structure consisting of VO5 polyhedra in which the V4+ would be predominantly isolated species, and any interactions between the V4+ ions would result from superexchange interactions through V–O–V bonds.