The potential of a novel alpha-Fe2O3/polyacrylonitrile (PAN) hybrid composite adsorbent to eliminate methylene blue (MB) from aqueous solution was evaluated. PAN was selected as the base composite. The presence of alpha-Fe2O3 as nanophotocatalyst on the surface of PAN introduced an efficient photocatalytic hybrid composite adsorbent for degrading MB. Effects of alpha-Fe2O3 nanopowder loading, pH, temperature, MB initial concentration, solar light, and contact time were investigated. Langmuir, Freundlich, and Temkin isotherms were applied to analyze the adsorption behavior. The Freundlich equation provided the best correlation with experimental data. Pseudo-first-order, pseudo-second-order, and intraparticle models were employed. Thermodynamic studies indicated an endotherm and spontaneous adsorption process in a defined temperature range.