An extensive study has been carried out to analyze and predict changes in the structure and elastic properties of the 10Li2O–(90−x)B2O3–xV2O5 glass system over the composition range 5≥x≥25 mol%. The anomalous behaviour between molar volume and density, besides changes in the fractal bond connectivity, average crosslink density, packing density and glass dissociation energy per unit volume have been interpreted in terms of the basic structural units that constitute the glass network. The applicability of Makishima–Mackenzie’s theory and the Rocherulle et al model has also been tested by studying the correlation between theoretical and experimental elastic moduli and Poisson’s ratio. The forward relationship between elastic moduli and packing density was achieved on the basis of Rocherulle et al. The estimated average crosslink density and dissociation energies per unit volume for BO4, BO3, VO4 and VO5 groups play an important role in predicting the physical and elastic properties. Both Makishima-Mackenzie’s theory and the Rocherulle et al model are valid for the majority of the investigated glass samples. Compared to Makishima-Mackenzie’s theory,(12,13) the Rocherulle et al model(14) is more suitable for predicting the bulk modulus and Poisson’s ratio of 10Li2O–(90−x)B2O3– xV2O5 glasses as well as the Young’s modulus, longitudinal modulus, bulk modulus and Poisson’s ratio of pure B2O3 glass. The validity of Makishima-Mackenzie’s theory for 10Li2O–(90−x)B2O3–xV2O5 glasses is much better than its validity for xLi2O–60B2O3–(40−x)V2O5 or xLi2O–(90−x)B2O3–10V2O5 glasses.