Designing adsorption materials with high adsorption capacities and selectivities is highly desirable for precious metal recovery. Desorption performance is also particularly crucial for subsequent precious metal recovery and adsorbent regeneration. Herein, a metalorganic framework (MOF) material (NH 2 -UiO-66) with an asymmetric electronic structure of the central zirconium oxygen cluster has an exceptional gold extraction capacity of 2.04 g g À 1 under light irradiation. The selectivity of NH 2 -UiO-66 for gold ions is up to 98.8 % in the presence of interfering ions. Interestingly, the gold ions adsorbed on the surface of NH 2 -UiO-66 spontaneously reduce in situ, undergo nucleation and growth and finally achieve the phase separation of highpurity gold particles from NH 2 -UiO-66. The desorption and separation efficiency of gold particles from the adsorbent surface reaches 89 %. Theoretical calculations indicate that -NH 2 functions as a dual donor of electrons and protons, and the asymmetric structure of NH 2 -UiO-66 leads to energetically advantageous multinuclear gold capture and desorption. This adsorption material can greatly facilitate the recovery of gold from wastewater and can easily realize the recycling of the adsorbent.