Cloud point extraction is a separation and preconcentration procedure that has been extensively applied for trace metal determination in several different matrices. Its major advantages are simple experimental procedures, low cost, high preconcentration factors, and environmental safety. These aspects include it in a set of analytical methods in agreement with the "green chemistry" principles. The surfactants characteristics and the process of micelle formation are outlined for a better understanding of the technique. After general considerations about the cloud point extraction basis and its extraction mechanism for metal chelates are considered, selected spectro-analytical techniques and their application for analysis of the micellar phase are discussed. The micellar extraction in metal speciation analysis, the on-line incorporation of cloud point extraction to flow injection analysis, and coupling with capillary electrophoresis are described. 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