Vanadium-containing glasses have aroused interest in several fields such as electrodes for energy storage, semiconducting glasses, and nuclear waste disposal. The addition of V2O5, even in small amounts, can greatly alter the physical properties and chemical durability of glasses; however, the structural role of vanadium in these multicomponent glasses and the structural origins of these property changes are still poorly understood. We present a comprehensive study that integrates advanced characterizations and atomistic simulations to understand the composition-structure-property relationships of a series of vanadium-containing aluminoborosilicate glasses. UV-vis spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption near-edge structure (XANES) have been used to investigate the complex distribution of vanadium oxidation states as a function of composition in a series of six-component aluminoborosilicate glasses. High-energy X-ray diffraction and molecular dynamics simulations were performed to extract the detailed short- and medium-range atomistic structural information such as bond distance, coordination number, bond angle, and network connectivity, based on recently developed vanadium potential parameters. It was found that vanadium mainly exists in two oxidation states: V5+ and V4+, with the former being dominant (∼80% from XANES) in most compositions. V5+ ions were found to exist in 4-, 5-, and 6-fold coordination, while V4+ ions were mainly in 4-fold coordination. The percentage of 4-fold-coordinated boron and network connectivity initially increased with increasing V2O5 up to around 5 mol % but then decreased with higher V2O5 contents. The structural role of vanadium and the effect on glass structure and properties are discussed, providing insights into future studies of sophisticated structural descriptors to predict glass properties from composition and/or structure and aiding the formulation of borosilicate glasses for nuclear waste disposal and other applications.