Methods for recovering gold from gold-bearing materials are provided. The methods rely upon on the self-assembly of KAuBr4 and α-cyclodextrin (α-CD) in aqueous solution to form a co-precipitate, a 1:2 complex, KAuBr4•(α-CD)2 (“α•Br”), either alone or in an extended {[K(OH2)6][AuBr4]⊂(α-CD)2}n chain superstructure (FIG. 1). The co-precipitation of α•Br is selective for gold, even in the presence of other metals, including other square-planar noble metals. The method enables one to isolate gold from gold-bearing materials from diverse sources, as further described.