Silver/silver chloride (Ag/AgCl) composites with a novel flower-like morphology were prepared via a hot precipitation assisted by the vinyl acetate monomer (VAM) route. An aqueous solution of AlCl3 was mixed with the vinyl acetate monomer and acetic acid before adding a AgNO3 solution at a temperature of 100 degrees C. The octapod shaped flower-like Ag/AgCl particles (or "flower-like Ag/AgCl" hereinafter) has eight petals each of which was about 7-11 pm in length. The flower-like octapods were formed by preferential overgrowth along the < 111 > directions of the cubic seeds. Detailed studies of the growth process at different AlCl3 concentrations revealed that the concave cube developed into a Rubik's cube where eight corners grew further into the flower-like structures. The VAM and acetic acid concentration strongly affected the growth of the Ag/AgCl to the flower-like structure and their optimum concentrations were determined. The morphologies of these particles were carefully examined by scanning electron microscopy (SEM). The crystal structures and orientation relationship were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible diffused reflectance spectroscopy (DRS). The flower-like Ag/AgCl microcrystals were tested for their photocatalytic degradation of orange G dye (OG) catalyzed by visible light. From comparative test runs, the flower-like Ag/AgCl exhibited better photocatalytic activity than simple and commercial Ag/AgCl particles. (C) 2015 Elsevier B.V. All rights reserved.