The preparation of a variety of salt complexes of [12-MC(Mn(III)N(shi))-4] (1) provides the structural basis for the first quantitative investigation of the cation and anion selectivity of metallacrowns. The preparation, X-ray crystal structures, and solution integrities of crystalline salts (LiCl2)[12-MC(Mn(III)N(shi))-4](-) ([(LiCl2). 1](-)), (Li(trifluoroacetate))]12-MC(Mn(III)N(shi))-4] ([(LiTFA). 1]), (Li)[12-MC(Mn(III)N(shi))-4](+) ([(Li). 1](+)), (NaBr)(2)[12-MC(Mn(III)N(shi))-4] ([(NaBr)(2) . 1]), and (KBr)(2)[12-MC(Mn(III)N(shi))-4] ([(KBr)(2) . 1]) of the metallacrown [12-MC(Mn(III)N(shi))-4] (1) are described. Each salt complex of the metallacrown forms from a generic one-step, high-yield synthesis giving 1:1 metal:metallacrown adducts with lithium and 2:1 metal:metallacrown complexes with sodium and potassium ions. On the basis of synthetic preference, the trend for the cation affinity is Li+ > Na+ > K+ and that for anion affinity is Cl- > Br- > TFA(-) > F- approximate to I-3(-). The 12-metallacrown-4, structural parameters compare favorably with those of 12-crown-4, an organic crown ether, as well as with those of the topologically similar alkali metal complexes of porphyrin and phthalocyanine dianions, solidifying the structural analogy between metallacrowns and crown ethers.