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Abstract: A set of polymers was imprinted with (+)-ephedrine at ambient and 10 bar pressure. The performance of the synthesized materials was studied by HPLC at six different temperatures: 0, 10, 20, 30, 40, and 50 °C. It was shown that the polymer morphology (surface area and porosity) and enantioselective properties are different for these two polymers an unexpected result which was in contradiction with the theoretical forecasts. A possible mechanism which explains the observed phenomenon is discussed. The contributing factor which influenced the polymer performance was the polymer swelling. This shows that, in addition to temperature, other physical parameters such as pressure and polymer swelling should be analyzed and accounted for in the quality control of MIP synthesis and application.