Supported Liquid Membranes (SLMs) have been widely studied as feasible alternative to traditional processes for separation and purification of various chemicals both from aqueous and organic matrices. This technique offers various advantages like active transport, possibility to use expensive extractants, high selectivity, low energy requirements and minimization of chemical additives. SLMs are not yet used at large scale in industrial applications, because of the low stability. In the present paper, after a brief overview of the state of the art of SLM technology the facilitated transport mechanisms of SLM based separation is described, also introducing the small and the big carrousel models, which are employed for transport modeling. The main operating parameters (selectivity, flux and permeability) are introduced. The problems related to system stabilization are also discussed, giving particular attention to the influence of membrane materials (solid membrane support and organic liquid membrane (LM) phase). Various approaches proposed in literature to enhance SLM stability are also reviewed. Modification of the solid membrane support, creating an additional layer on membrane surface, which acts as a barrier to LM phase loss, increases system stability, but the membrane permeability, and then the flux, decrease. Stagnant Sandwich Liquid Membrane (SSwLM), an implementation of the SLM system, results in both high flux and stability compared to SLM. Finally, possible large scale applications of SLMs are also reviewed, evidencing that if the LM separation process is opportunely carried out (no production of byproducts), it can be considered as a green process.