Gold is an essential precious metal with exceptional properties. Thus, azole-functionalized microspheres (PS-3-AT) were prepared by grafting 3-amino-1,2,4-triazole (3-AT) into chloromethyl polystyrene beans (PS-Cl) and used as a novel adsorbent for the gold(I)-thiosulfate complex. The effects of initial gold concentration, thiosulfate concentration, temperature, and pH on the Au(S2O3)23- adsorption process over PS-3-AT were investigated. In this study, PS-3-AT was considered an effective adsorbent for Au(I) recovery from a thiosulfate solution, demonstrating that PS-3-AT completely adsorbed Au(S2O3)23- with an adsorption capacity of 39.8 kg t-1 achieved during multistage adsorption testing. Through adsorption kinetics and isotherm studies, the pseudo-second-order and Freundlich models well describe the adsorption process of PS-3-AT for Au(I), also suggesting the exothermic nature. Furthermore, SEM, FT-IR spectroscopy, BET, and XPS techniques were used to characterize the surface and structural properties of the samples. Notably, a reliable adsorption mechanism was developed that proposed the formation of the -NH+Cl- group during the grafting process and Cl- exchange with Au(S2O3)23- to achieve Au(I) capture. Moreover, quantum chemistry calculations and the independent gradient model (IGM) were adopted to visualize the interaction between PS-3-AT and Au(S2O3)23- at an atomic level. The desorption ratio was 97.9% while 2 M NaCl was used as the desorbent, and regeneration with PS-3-AT was achieved after five cycles. Therefore, the facile synthetic method and adsorption properties of PS-3-AT for the gold(I)-thiosulfate complex are satisfactory, which is valuable for the development of thiosulfate gold leaching technologies.