To overcome the limitations of the detection systems associated with gas or liquid chromatography, a sample pretreatment is required with the objective to provide a sample fraction enriched with all the target analytes and as free as possible from other matrix components. There is now no doubt that solid-phase extraction (SPE) has now become the method of choice for carrying out simultaneously the extraction and concentration of many compounds in aqueous samples. Many recent applications of SPE to multiresidue analysis are reviewed with an emphasis on the importance of the choice of the sorbent and of the sample volume. SPE is particularly well adapted to multiresidue analysis including compounds from a wide range of polarity or characterized by various physico-chemical properties. However, SPE is not completely free from practical problems inherent to the nature of the compounds or to the coupling to the chromatographic systems. Many examples are reported to illustrate these problems which can in most cases be circumvented. New developments in SPE are also reviewed.