This review focuses on the combination of elemental detection techniques with liquid-phase microextraction (LPME), namely, single drop microextraction, hollow fiber based liquid-phase microextraction, dispersive liquid-liquid microextraction, and related techniques. General features of different microextraction procedures, historical overview and automation of LPME are described and compared, along with examples of new developments and applications presented to demonstrate its potential for trace and ultra-trace metal analysis. Furthermore, potential applications and an outlook on the combination of LPME and elemental detection techniques for inorganic analysis are presented. The authors would like to thank the Spanish Ministry of Economy and Competitiveness and European Union (FEDER funds) (project n. CTQ2016-79991-R) for the financial support. P. Baile also thanks Ministry of Education, Culture and Sports for her FPU grant (FPU14/04589).