Improved methods for achieving the selective extraction of lithium salts from lithium sources, including rocky ores, salt-lake brines, and end-of-life lithium-ion batteries, could help address projected increases in the demand for lithium. Here, we report an ion pair receptor (2) capable of extracting LiCl and LiBr into an organic receiving phase both from the solid state and from aqueous solutions. Ion pair receptor 2 consists of a calix[4]pyrrole framework, which acts as an anion binding site, linked to a phenanthroline cation binding motif <i>via</i> ether linkages. Receptor 2 binds MgBr₂ and CaCl₂ with high selectivity over the corresponding lithium salts in a nonpolar aprotic solvent. The preference for Mg²⁺ and Ca²⁺ salts is reversed in polar protic media, allowing receptor 2 to complex LiCl and LiBr with high selectivity and affinity in organic media containing methanol or water. The effectiveness of receptor 2 as an extractant for LiCl and LiBr under liquid-liquid extraction (LLE) conditions was found to be enhanced by the presence of other potentially competitive salts in the aqueous source phase.