Separation and recycling of rare-earths using ionic liquids as extractant are becoming a promising approach to replace traditional volatile organic solvents in recent years. Generally, the addition of some special salts could improve the extraction efficiency of rare-earths by numerous non-functional ionic liquids. However, knowledge behind the nature of the salt effect is limited. Here, we found that the enhancement in the extraction of rare-earth ions, Pr3+ ions, using non-functional ionic liquid, [A336] [NO3] (Tricaprylmethylammonium nitrate) was driven by the synergism of Hofmeister bias and complexation behaviors of salt anions with Pr3+ ions. Molecular dynamic simulations offered a new insight into the interaction mechanism of the ionic liquid with Pr3+ ions at liquid/liquid interface. It was revealed that salt anions could perform as a bridge to connect Pr3+ ions and the ionic liquid, so that promoted the extraction of Pr3+ ions. Therefore, the strong complexation ability of salt anions with Pr3+ ions and poor hydration of salt anions faciliated the transport of Pr3+ ions across liquid/liquid interface. (C) 2018 Elsevier Inc. All rights reserved.