A series of polymer-supported ZnO nanocomposites (NCs) were prepared by solution cast method and their optical properties, phase formation and structure morphology were characterized by UV-Vis DRS analysis, powder X-ray diffraction, optical microscopy, scanning electron microscopy, respectively. The morphology of the newly synthesized composite was confirmed as porous nature with granular network structure using optical microscopy and SEM analysis and demonstrated a good crystalline growth with hexagonal phase exhibiting a crystallinity size of the ZnO of 37.3 nm. The addition of V2O5 significantly altered the band gap, 3.16-3.11 eV. For the very first time, the photodegradation of different classes of azo dyes, using prepared polymer NCs as a photocatalyst was investigated under UV light irradiation. The complete degradation of the dye solution was observed for 160 and 80 min and the optimum condition for the effective degradation was observed. Interestingly, the present photocatalytic system was very faster than that of other ZnO-based polymer NCs photocatalyst. The roles of V2O5 addition, degradation mechanism as well as catalyst stability in the photoreaction were comprehensively studied. The crucial role of V2O5 addition in the ZnO-based polymer was improved photocatalytic activity which is mainly attributed to the superior electron transfer ability, enhanced light harvesting and boosted catalytic active sites. The photo-induced holes were considered to be the dominant active species in the photodegradation process. Comparatively, the present reported catalytic systems were simple, reusable and effective models for the degradation of dye-polluted water from the large-scale industries.