A comprehensive review of the sequential extraction schemes for metal fractionation in environmental samples (ie., sediment, soil, sewage sludge, fly ash, etc.) is presented. The review contains more than 400 references and covers principally the literature published over the last decade. The use of each reagent involved in these schemes is looked at critically, and guidelines for their selectivity and extraction capacity are given. The operational character of these schemes is emphasised. Topics such as comparability between sequential extraction schemes of widespread use, harmonisation, acceleration, validation, etc. are addressed and future developments outlined.