Adsorption is an efficient and highly selective method for gold recovery. Introducing rich N/S organic groups to combine with metal-organic frameworks (MOFs) as adsorbents is regarded as a practical and efficient approach to enhance gold recovery. Herein, a MOF (zirconium isothiocyanatobenzenedicarboxylate MOF, UiO-66-NCS) was designed to combine with amidinothiourea (AT) to form UiO-66-AT (zirconium amidothiourea-benzenedicarboxylate MOF) for efficient and rapid adsorption. The prepared UiO-66-AT delivers an improved adsorption capacity (about 903.02 mg/g at 1000 mg·L-1 of the initial Au3+) and an impressive adsorption rate within minutes (about 10 min for 200 mg·L-1 Au3+). Meanwhile, it exhibits sustainable stability after 5 cycles with a retention rate of 99.52% and excellent adsorption selectivity of 98.76% in actual wastewater. According to advanced characterizations and Density Functional Theory (DFT) simulation, the mechanism might be elaborated as electrostatic adsorption, chelating coordination, and chemical reduction. The modified active groups of the MOF provide the adsorption sites for Au(III) and the rapid reduction of Au(0). UiO-66-AT maintains a large adsorption capacity and high surface reduction activity while realizing stable application in multiple cycles, which is of good practical application value.