The metal extraction mechanism of basic extractants is typically described as an anion exchange process, but this mechanism does not correctly explain all observations. This paper introduces a novel model for the extraction of metals by basic extractants from chloride media supported by experimental data on methyltrioctylammonium chloride and Aliquat 336 chloride systems. This model relies on the hypothesis that the metal species least stabilized in the aqueous phase by hydration (i.e., the metal species with the lowest charge density) is extracted more efficiently than the more water stabilized species (i.e., species with higher charge densities). Once it is transferred to the organic phase, the extracted species can undergo further Lewis acid-base adduct formation reactions with the chloride anions available in the organic phase to form negatively charged chloro complexes, which than associate with the organic cations. Salting-out agents influence the extraction, most likely by decreasing the concentration of free water molecules, which destabilizes the metal complex in the aqueous phase. The evidence provided includes (1) the link between extraction and transition-metal speciation, (2) the trend in extraction efficiency as a function of the concentration of different salting-out agents, and (3) the behavior of HCl in the extraction system. The proposed extraction model better explains the experimental observations in comparison to the anion exchange model and allows the prediction of optimal conditions for metal extractions and separations a priori, by selecting the most suitable salting-out agent and its concentration.