Lightweight, metal‐free, sustainable, and reusable adsorbent materials are of paramount significance in addressing the challenges of wastewater treatment. Accordingly, semi‐crystalline nanocellulose (NC) is extracted from tissue paper waste and used to modify polyacrylonitrile (PAN) to produce electrospun nanowebs with strand diameters from ≈180–300 nm. The incorporation of NC into PAN is confirmed by infrared and Raman spectroscopy and X‐Ray diffraction. When tested for crystal violet (CV) adsorption, NC‐modified PAN (20% NC@PAN) exhibits the highest CV removal capacity, achieving 91–94% removal over three cycles each, demonstrating exceptional recyclability. In contrast, unmodified PAN significantly decreases in CV adsorption capacity (from 59% to 48% in the third cycle), possibly due to an increased (≈36%) nanofiber diameter. The adsorption kinetics, exhibiting pseudo‐second order, interparticle (in between nanofibers) diffusion, and Elovich kinetic models emphasize the role of multilayer CV adsorption through reversible chemical interactions. Confocal micro‐Raman spectroscopy unveils a multifaceted CV adsorption mechanism, suggesting both surface and multilayer diffusion, with NC‐enhancing interactions. These findings demonstrate the potential of NC‐modified PAN nanowebs as effective and environmentally sustainable adsorbents for removing CV from aqueous solutions, suggesting promising practical applications.