The complexes [M(L)][BAr^F] (BAr^F = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), L = [18]aneO₄S₂ (1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane): M = Li–Cs; L = [18]aneO₂S₄ (1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane): M = Li, Na, K; L = [18]aneO₄Se₂ (1,4,10,13-tetraoxa-7,16-diselenacyclooctadecane): M = Na, K, as well as [Na(18-crown-6)][BAr^F], are obtained in good yield as crystalline solids by reaction of M[BAr^F] with the appropriate macrocycle in dry CH₂Cl₂. X-ray crystallographic analyses of [Li([18]aneO₄S₂)][BAr^F] and [Li([18]aneO₂S₄)][BAr^F] show discrete distorted octahedral cations with hexadentate coordination to the macrocycle. The heavier alkali metal complexes all contain hexadentate coordination of the heterocrown, supplemented by M⋯F interactions via the anions, producing extended structures with higher coordination numbers; Na: CN = 7 or 8; K: CN = 8; Rb: CN = 9; Cs: CN = 8 or 10. Notably, all of the structures exhibit significant M–S/Se coordination. The crystal structures of the potassium and rubidium complexes show two distinct [M(heterocrown)]⁺ cations, one with M⋯F interactions to two mutually cis [BAr^F]⁻ anions, and the other with mutually trans [BAr^F]⁻ anions, giving 1D chain polymers. Solution multinuclear (¹H, ¹³C, ⁷Li, ²³Na, ¹³³Cs) NMR data show that the macrocyclic coordination is retained in CH₂Cl₂ solution.