Metal oxides (MO) are widely preferred for removing various effluents from water and air, however due to poor utilization of visible light, the application of MO nanoparticles for water treatments is hindered. This work reports the synthesis of ring structured PVA-assisted Fe2O3 (P-Fe2O3) nanocomposite through green route synthesis, for the elimination of methylene blue via Sunlight triggered photocatalyst. FTIR spectroscopy confirmed the presence of desired functional groups in novel ring structured Fe2O3 and PVA-assisted Fe2O3 (P-Fe2O3) nanocomposite. The crystallinity of Fe2O3 was also studied through XRD. Surface topography of Fe2O3 was examined through FE-SEM, that reveals a central hole with extended surface area of Fe2O3. UV–vis-spectroscopy is used to evaluate photocatalytic efficiency which shows, pristine Fe2O3 exhibited 27% degradation in stipulated time intervals of 30∼120 mins. The photocatalytic efficiency of augmented P-Fe2O3 nanocomposite expelled 82% of the methylene blue in span of just 02 hrs. The stability of the developed nanocomposite in the effluent medium was investigated through FTIR by observing the change in carboxyl adsorption band produced during degradation of PVA, that manifests the fact that no degradation was witnessed for PVA even after 120 min, that makes P-Fe2O3 a promising material for the degradation of azo dyes.