As the gap between lithium supply and demand continues to widen, the need to develop ion-selective technologies, which can efficiently extract lithium from unconventional water sources, grows increasingly crucial. In this study, we investigated the fundamentals of applying a solid-state electrolyte (SSE), typically used in battery technologies, as a membrane material for aqueous lithium extraction. We find that the anhydrous hopping of lithium ions through the ordered and confined SSE lattice is highly distinct from ion migration through the hydrated free volumes of conventional nanoporous membranes, thus culminating in unique membrane transport properties. Notably, we reveal that the SSE provides unparalleled performance with respect to ion-ion selectivity, consistently demonstrating lithium ion selectivity values that are immeasurable by even the part-per-billion detection limit of mass spectrometry. Such exceptional selectivity is shown to be the result of the characteristic size and charge exclusion mechanisms of solid-state ion transport, which may be leveraged in the design of next-generation membranes for resource recovery.