The synergistic combination of ionic liquids (ILs) and single-drop microextraction (SDME) involves a powerful coupling toward the development of sustainable analytical methodologies. This overview provides a survey of the literature regarding IL-SDME, including a database on relevant physicochemical properties of ILs for their application in SDME, the strategies implemented to combine IL-based SDME methods efficiently with analytical instrumentation, and a critical evaluation of the analytical applications involving IL-based SDME methodologies. Overall, this work identifies current inefficiencies, challenges and opportunities of this convenient, yet underexploited, analytical approach.