In the present work, an essential advance in the preparation of novel nanocomposites based on functionalized V₂O₅ nanostructures with reduced graphene oxide by hydrothermal method, which has great potential for use in photocatalytic processes related to environmental remediation. XRD analysis confirmed V₂O₅ in an orthorhombic structure. SEM images showed transparent RGO layers well anchored onto the surface of the V₂O₅ with a homogeneous distribution. Raman spectroscopy further explained the hybridization and interaction between the components. The photocatalytic activity of Rhodamine-B in aqueous solutions has been studied upon irradiation with visible light. A high RhB degradation was obtained using the V₂O₅/RGO photocatalyst (82 %), compared to the degradation obtained with only V₂O₅ (60 %). First-principles Density Functional Theory (DFT) simulations reveal a strong interaction between V₂O₅ molecules and graphene surfaces, with an adsorption energy of −1.673 eV and a significant charge transfer of 0.367 e− to RGO. This interaction modifies the electronic structure, creating semi-metallic behavior near the Fermi level and enhancing catalytic activity through improved charge carrier dynamics and active sites for photocatalytic applications.