The stability of polymer inclusion membranes (PIMs) relative to other liquid membranes is amongst the major reasons for the recent rejuvenation of interest in carrier-mediated transport for selective separation and recovery of metal ions as well as numerous organic solutes. This is reflected by an increasing number of PIM investigations reported in the literature over the last two decades. Given the outstanding performance of PIMs compared to other types of liquid membranes particularly in terms of membrane lifetime, it has been predicted that practical industrial applications of PIMs will be realized in the near future. This review provides a comprehensive summary of the current knowledge relevant to PIMs for the extraction and transport of various metal ions and small organic solutes. PIM studies reported to date are systematically summarized and outlined accordingly to the type of carriers used, i.e. basic, acidic and chelating, neutral or solvating, and macrocyclic and macrornolecular. The paper reviews the various factors that control the transport rate, selectivity and stability of PIMs. The transport phenomena observed by various authors are related to the membrane characteristics, physicochemical properties of the target solutes as well as the chemistry of the aqueous solutions making up the source and receiving phases. The results from these studies reveal an intricate relationship between the above factors. Furthermore, while the interfacial transport mechanisms in PIMs are thought to be similar to those in supported liquid membranes (SLMs), the bulk diffusion mechanisms in PIMs governing their permeability and selectivity require better understanding. This review also delineates two mathematical modeling approaches widely used in PIM literature: one uses a set of assumptions that allow the derivation of analytical solutions valid under steady-state conditions only; the other takes into account the accumulation of the target species in the membrane during the initial transport state and therefore can also be applied under non-steady-state conditions. The latter is essential when the interfacial complexation reaction kinetics is slow. It involves more complex mathematics and requires the application of numerical techniques. The studies included in this review highlight the potential of PIMs for various niche applications on a practical scale. The discussions provided, however, also emphasize the need for more fundamental research before any such practical applications of PIMs can be realized. This is specifically important for small organic compounds because to date scientific investigation involving the extraction and transport of these compounds remains limited. Transport mechanisms of small organic compounds are less well understood and are likely to be more complex than those observed with the transport of metal ions. (c) 2006 Elsevier B.V. All rights reserved.