Silicone elastomer (in the form of a flexible rod) is one of the materials currently tested for use in analytical extraction techniques and passive sampling devices. We investigated the applicability of this material for the enrichment of selected polar pharmaceuticals (antipyrine, carbamazepine, diclofenac, ibuprofen, bezafibrate) from water. Time-resolved batch extraction tests (up to five weeks in duration) were performed in stirred water samples (∼0.5 L) with 2-cm-long silicone rod pieces. After re-extraction of trapped compounds with methanol, analysis was performed using liquid chromatography coupled with mass spectrometry. Distribution equilibrium was reached after a test duration of seven days. The silicone rod/water partition coefficients of the investigated pharmaceuticals range from 4 (antipyrine) to 1250 (diclofenac), and are related to the hydrophobicity of the compound. Enrichment of these pharmaceuticals in the silicone rod is lower than for other compound classes (chlorinated and polycyclic hydrocarbons).