Liquid-phase microextraction (LPME) emerged in the mid-to-late 1990s, facing up to the main shortcomings of the classical liquid-liquid extraction. Since its origin, this new technique has been in continuous development driven by its successful and widespread use in the analytical sciences. Its inherent properties, such as low sample volume requirement, high preconcentration factors achieved and excellent sample clean-up, make LPME a very useful technique for bioanalytical sample preparation. This review focuses on the main LPME-related techniques, predominantly single-drop microextraction and supported hollow-fiber LPME, paying particular attention to the bioanalytical applications. A general view of the essential trends, including the description of promising extraction modes and solvents, is also highlighted.