The burgeoning demand for lithium across various sectors, most notably in lithium-ion batteries, necessitates the development of efficient extraction and purification methodologies. As a response to this imperative, the design of synthetic receptors exhibiting high selectivity and affinity for lithium ions has emerged as a crucial area of research. This investigation proposes a simple and effective approach to high-performance lithium receptors that capitalizes on ion-dipole interactions as the principal driving force for lithium binding. Our investigation encompasses the design, synthesis, and evaluation of five distinct ionophores characterized by varied ion-dipole interactions with lithium, culminating in significantly enhanced binding affinity and Li + /Na + selectivity compared to conventional macrocyclic crown ether-based receptors. Moreover, we identify a new building block based on pyridine- N -oxide, which serves as an efficacious motif for developing receptors with augmented lithium-binding capacities. Additionally, our findings demonstrate a rapid and efficient solid-liquid extraction process for LiCl in the presence of a substantial excess of NaCl and KCl, employing the newly discovered ionophore. Collectively, this study contributes valuable insights into molecular design strategies for high-performance lithium receptors and advocates for continued exploration of sustainable molecular materials to enhance lithium recognition and extraction efficiencies. Incorporating strong ion-dipole interactions within acyclic molecular frameworks can remarkably enhance both binding affinity and selectivity for lithium ion, offering a simple and effective strategy for developing high-performance lithium receptors.