Persistently high arsenic levels in drinking water threaten underprivileged areas worldwide. Although nanomaterials exhibit exceptional arsenic removal properties, their implementation presents challenges. We converted N-methylimidazole-modified polyvinyl chloride into a granular anion exchange resin (PNAXRs) using an environmentally friendly and gentle synthesis method. Additionally, a unified approach for embedding nanomaterials within these resins was proposed, yielding a TiO2 composite resin (TiO2@PNAXRs). Structural characterization confirmed the successful grafting of imidazolium cations with anion-exchange properties onto polyvinyl chloride side chains. BET analysis indicates a high specific surface area of 70.31 m2/g for the PNAXRs. TGA curves demonstrate the successful encapsulation of approximately 24.9% TiO2 within the composite resin. The SEM-EDS results show a uniform distribution of TiO2 in the PNAXRs, which facilitates the effective utilization of TiO2. Adsorption experiments in conjunction with XPS analysis provided insights into the dual role of inner-sphere complexation and ion exchange in the adsorption mechanism of As(V) by TiO2@PNAXRs. In dynamic adsorption tests utilizing high-As(V) groundwater from the Datong Basin as the influent, TiO2@PNAXRs demonstrated the ability to produce effluents that meet the World Health Organization's recommended limit for arsenic in drinking water, with a capacity of 1780 bed volumes. These findings support the use of PNAXRs as ideal matrices for TiO2 and their practical application in As(V) removal processes.