Herein, we report an alkali metal cation-dependent approach to gold recovery, facilitated by second-sphere coordination with eco-friendly alpha-cyclodextrin (alpha-CD). Upon mixing eight salts composed of Na+, K+, Rb+, or Cs+ cations and [AuX4](-) (X = Cl/Br) anions with alpha-, beta-, or gamma-CD in water, co-precipitates form selectively from the three (out of 24) aqueous solutions containing alpha-CD with KAuBr4, RbAuBr4, and CsAuBr4, from which the combination of alpha-CD and KAuBr4 affords the highest yield. Single-crystal X-ray analyses reveal that in 20 of the 24 adducts CD and [AuX4](-) anions form 2:1 sandwich-type second-sphere adducts driven partially by [C-H center dot center dot center dot X-Au] interactions between [AuX4](-) anions and the primary faces of two neighboring CDs. In the adduct formed between alpha-CD and KAuBr4, a [K(OH2)(6)](+) cation is encapsulated inside the cavity between the secondary faces of two alpha-CDs, leading to highly efficient precipitation owing to the formation of a cation/anion alternating ion wire residing inside a continuous alpha-CD nanotube. By contrast, in the other 19 adducts, the cations are coordinated by OH groups and glucopyranosyl ring O atoms in CDs. The strong coordination of Rb+ and Cs+ cations by these ligands, in conjunction with the stereoelectronically favorable binding of [AuBr4](-) anions with two alpha-CDs, facilitates the co-precipitation of the two adducts formed between alpha-CD with RbAuBr4 and CsAuBr4. In order to develop an efficient process for green gold recovery, the co-precipitation yield of alpha-CD and KAuBr4 has been optimized regarding both the temperature and the molar ratio of alpha-CD to KAuBr4.