A series of the novel Ag/AgCl/ZnO nano-networks with different Ag contents had been synthesized by combining coordination-precipitation with calcination method and characterized by different techniques. According to the characterization results and the colloidal balance theory, the two-step growth mechanism had been proposed for explaining the formation of Ag/AgCl/ZnO nano-networks. The Ag/AgCl/ZnO nano-networks exhibited excellent photocatalytic activity for photodegradation of methyl orange (MO) under ultraviolet (UV), simulation sunlight and sunlight irradiation. The optimal Ag loading content is around 1.35 wt.%, and the MO solution was completely degraded by Ag/AgCl/ZnO after 30, 50, 120 min under UV, simulated sunlight, and sunlight, respectively. In addition, the photocatalytic mechanism of Ag/AgCl/ZnO nano-networks was illustrated and discussed. (C) 2015 Elsevier B.V. All rights reserved.