In this article, the scientific literature on electromembrane extraction (EME) of polar substances (log P < 2) is reviewed. EME is an extraction technique based on electrokinetic migration of analyte ions from an aqueous sample, across an organic supported liquid membrane (SLM), and into an aqueous acceptor solution. Because extraction is based on voltage-assisted partitioning, EME is fundamentally suitable for extraction of polar and ionizable substances that are challenging in many other extraction techniques. The article provides an exhaustive overview of papers on EME of polar substances. From this, different strategies to improve the mass transfer of polar substances are reviewed and critically discussed. These strategies include different SLM chemistries, modification of supporting membranes, sorbent additives, aqueous solution chemistry, and voltage/current related strategies. Finally, the future applicability of EME for polar substances is discussed. We expect EME in the coming years to be developed towards both very selective targeted analysis, as well as untargeted analysis of polar substances in biomedical applications such as metabolomics and peptidomics.