In this work, we have synthesized hexapods AgCl crystals with mace pods for the first time. Diallyldimethylammonium chloride (DDA)-controlled stepwise evolution of AgCl crystals from octahedron to hexapods with mace pods are achieved by one-pot method. The intermediates have been captured which show the basic process of crystal growth. In this process, octahedra AgCl crystals firstly grow along the <100> direction and then change to grow in the <110> direction. At the same time, the size of AgCl grow from 2 μm to 20 μm. Due to the poor absorption of visible light by AgCl, sodium borohydride(NaBH4) is used to reduce AgCl hexapods with mace pods crystals. By changing the mole ratio(R) of NaBH4 to AgCl, the new structure was reduced to obtain a series of Ag@AgCl microstructures. Visible light catalysis effects of the Ag@AgCl microstructures on degradation of methyl orange (MO) were investigated. The Ag@AgCl microstructures with R = 0.02 have a high photocatalytic performance, which completely degrades MO in 40 minutes.