Molecularly imprinted polymers (MIP) are stable polymers with molecular recognition abilities, provided by the presence of a template during their synthesis, and are excellent materials with high selectivity for sample preparation in bioanalytical methods. This short review discusses aspects of MIP preparation and its applications as a sorbent material in pharmaceutical and biomedical analysis. MIP in different extraction configurations, including classical solid-phase extraction, solid-phase microextraction, magnetic molecularly imprinted solid-phase extraction, microextraction by packed sorbent and solid-phase extraction in pipette tips, are used to illustrate the good performance of this type of sorbent for sample preparation procedures of complex matrices, especially prior to bioanalytical approaches.