Density Functional Theory (DFT) studies were conducted to evaluate the sensing mechanism between benzene and a polymeric sensing material, referred to as SXFA, which contains trifluoro-groups and OH-groups. These studies were undertaken to improve the understanding of how benzene and SXFA mechanistically interact based on their chemistry, information which can be used to more efficiently design polymeric sensing materials. We find that benzene adsorbed onto the OH-groups in SXFA rather than the trifluoro-groups as previously proposed. Specifically, we find that sorption results from electrostatic attraction between the negative benzene ring and the positive hydrogens of the OH-groups of SXFA.