AbstractDeveloping an eco-friendly, efficient, and highly selective gold-recovery technology is urgently needed in order to maintain sustainable environments and improve the utilization of resources. Here we report an additive-induced gold recovery paradigm based on precisely controlling the reciprocal transformation and instantaneous assembly of the second-sphere coordinated adducts formed between β-cyclodextrin and tetrabromoaurate anions. The additives initiate a rapid assembly process by co-occupying the binding cavity of β-cyclodextrin along with the tetrabromoaurate anions, leading to the formation of supramolecular polymers that precipitate from aqueous solutions as cocrystals. The efficiency of gold recovery reaches 99.8% when dibutyl carbitol is deployed as the additive. This cocrystallization is highly selective for square-planar tetrabromoaurate anions. In a laboratory-scale gold-recovery protocol, over 94% of gold in electronic waste was recovered at gold concentrations as low as 9.3 ppm. This simple protocol constitutes a promising paradigm for the sustainable recovery of gold, featuring reduced energy consumption, low cost inputs, and the avoidance of environmental pollution.