Stir bar sorptive extraction (SBSE) is a miniaturized and solvent-less sample preparation method for extraction and concentration of organic compounds from aqueous samples. The method is based on sorptive extraction, whereby the solutes are extracted into a polymer, such as polydimethylsiloxane (PDMS), coated on a stir bar. Using an apolar PDMS coating, SBSE provides high recoveries for apolar solutes; however, SBSE recoveries for polar solutes are low. Although several more polar coatings for SBSE were developed, these extraction phases are mostly not compatible with thermal desorption (TD) and/or have inferior performance characteristics related to robustness, bleeding, stability, etc. compared to PDMS. In this perspective, two recently introduced SBSE approaches are described that can be used to extend the applicability of a PDMS coating to more polar solutes: (1) SBSE with freeze concentration [ice concentration linked with extractive stirrer (ICECLES)], which is based on the concentration of analytes by gradually reducing the phase ratio (sample/extraction phase), and (2) SBSE using a solvent-swollen PDMS [solvent-assisted SBSE (SA-SBSE)], which is based on a combination of polarity modification and volume increase by PDMS phase swelling using certain types of solvents while maintaining the original characteristics of the PDMS phase.