A conventional plasmonic Ag-AgCl photocatalyst consists of Ag nanoparticles (AgNPs) and AgCl. Here, we converted a small amount of Ag + on the surfaces of AgCl particles into single-atom Ag(0) (SAAg). SAAg was characterized with high-angle annular dark field aberration corrected (HAADF AC)-STEM and quantified with electron spin resonance (ESR). The obtained Ag EG /Mg(OH) 2 material was efficient and afforded excellent selectivity control between hydrodehalogenation and deiodination-borylation under visible light irradiation. SAAg acted as the 1e − -reducing site of the photocatalyst and its loading is linearly correlated with the initial reaction rate. While the quantity of SAAg was only 6.0 × 10 –8 mol g −1 , the TOF of SAAg reached 1.4 × 10 4 h −1 . The oxidation state of SAAg retained 0 in both the resting and the working states. This study suggests SAAg may be an effective cocatalyst in general for reductive dehalogenation of organic halides. • A plasmonic photocatalyst consisting of single-atom Ag(0) was prepared using a solvothermal method. • The photocatalyst showed high efficiency in reductive deiodination of aryl iodides under visible light irradiation. • Single-atom Ag(0) mediates the 1e − -reduction of aryl iodide molecules.