The liquid-phase microextraction based on solidification of floating organic drop (LPME-SFO), which incorporated sampling, extraction, and concentration into a single step, has been developed to be a new environmentally benign sample-preparation technique. This novel technique has proved to be low-cost and virtually organic solvent-free and could provide a high enrichment factor. It can be easily integrated with gas chromatography (GC), high-performance liquid chromatography (HPLC), and atomic absorption spectrometry (AAS). The basic principles and the main parameters that affect the extraction efficiency and recent applications of the LPME-SFO are briefly reviewed in this paper.