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Reversible bromoform adsorption on crystalline polyvinylidene fluoride with 30% of trifluoroethylene, P(VDF–TrFE 70:30) was examined by photoemission and inverse photoemission spectroscopies. The adsorption of bromoform on this polymer surface is associative and reversible. Molecular bromoform adsorption appears to be an activated process at 120 K with enhanced adsorption following the initial adsorption of bromoform. Strong intermolecular interactions are also implicated in the presence of a weak shake off or screened photoemission final state, whose intensity scales with the unscreened photoemission final state.