A large amount of gold in electronic waste (E-waste) is not properly recovered owing to the absence of efficient and safe leaching methods. Herein, we proposed the concept of ‘water-soluble organic Au leaching’ and created a new water-soluble organic leaching agent, WS NBS–DMF, by dissolving millimolar amounts of N-bromosuccinimide (NBS) and dimethylformamide (DMF) in water. Under mild conditions (25 ℃, pH 7.0), WS NBS–DMF achieved a 94.9 % leaching efficiency of Au for waste printed circuit board (WPCB) with limited leaching of base metals. The potent bromine radical (Br•) and ligands significantly contributed to Au complexation and oxidization via in situ bromine generation and radical initiation from WS NBS–DMF. The bidirectional hydrogen-bond effect of DMF facilitated the in situ bromine generation. Two Au(I) complexes ([AuBr2]- and [(NHS)AuBr]-) and an Au(III) complex ([(NHS)AuBr3]-) were confirmed as the Au leaching products by spectroscopy and mass spectrometry. Furthermore, reciprocal σ-donations between the Au center and ligands in the bonding orbitals enhanced the stability of the Au complexes, thereby promoting efficient Au leaching. Comparing with other leaching methods, this study of WS NBS–DMF provides a safe, economic and eco-friendly technique for efficient and selective gold recovery from e-waste.