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The recovery of lithium from global water resources continues to be challenging due to interfering metal ions with similar solution properties. Hence, a lithium-selective diblock copolymer system containing crown ethers (CEs) is developed. A polystyrene-block-poly(methacrylic acid) diblock copolymer is synthesized first via a one-pot solution-emulsion reversible addition-fragmentation chain transfer polymerization. A subsequent Steglich esterification yields the CE functionalized polymer. The complexation properties with different alkal