In this paper the most recent developments in the microextraction of polar analytes from aqueous environmental samples are critically reviewed. The particularities of different microextraction approaches, mainly solid-phase microextraction (SPME), stir-bar-sorptive extraction (SBSE), and liquid-phase microextraction (LPME), and their suitability for use in combination with chromatographic or electrically driven separation techniques for determination of polar species are discussed. The compatibility of microextraction techniques, especially SPME, with different derivatisation strategies enabling GC determination of polar analytes and improving their extractability is revised. In addition to the use of derivatisation reactions, the possibility of enhancing the yield of solid-phase microextraction methods for polar analytes by using new coatings and/or larger amounts of sorbent is also considered. Finally, attention is also focussed on describing the versatility of LPME in its different possible formats and its ability to improve selectivity in the extraction of polar analytes with acid-base properties by using separation membranes and buffer solutions, instead of organic solvents, as the acceptor solution.