Salt-assisted LLE (SALLE) has been attracting growing interest in bioanalysis. The technique is particularly advantageous due to its simple and fast experimental execution using conventional laboratory equipment. Besides, SALLE uses water-miscible organic solvents making the extracts readily compatible with various analytical separation and detection techniques. This article presents a brief overview of the extraction technique and its role in bioanalysis. Some of the most relevant achievements on SALLE application to biological samples are discussed - namely the study of the main extraction parameters, the combination with other extraction techniques and the instrumental analysis of the extracts. Developments on automation, miniaturization and microextraction for SALLE procedures are also discussed as a perspective for future applications even more attractive for the analysis of biological samples.