The sorption performance of hyper-cross-linked Macronet resin (MN200) to remove phenol and aniline from aqueous solution has been evaluated. Fixed bed column experiments were undertaken to obtain the breakthrough curves in both single and binary solutions. The film-surface diffusivity model has been used to predict the single (phenol and aniline) fixed bed breakthrough curves by using the Langmuir and Freundlich single isotherm data to represent the equilibrium. A good description of the experimental data has been obtained by both isotherms, and the mass transfer coefficient and the surface diffusivity have been obtained as optimized parameters for both solutes. The binary breakthrough curve prediction has been performed by the film surface diffusion model, incorporating an equilibrium relationship defined by the extended Langmuir isotherm model and the ideal sorbed solution theory (IAST). The sum of square errors (SSE) obtained for the IAST approach confirms the good agreement between the experimental and the predicted breakthrough data and the deviation obtained for the extended Langmuir model. The surface diffusivities in binary sorption reported a significant difference to those obtained in a single system, indicating that binary sorption is mainly controlled by the intraparticle diffusion.