In this study, we demonstrate a facile and novel dual-ion-exchange method together with subsequent visible-light induced reduction for synthesis of mesoporous BiVO4/Ag/AgCl ternary heterostructured microspheres (HSMSs) with uniform size distribution. Using flower-like BiOCl microspheres as the starting material, and introducing NaVO3 and AgNO3 by a facile impregnation method, mesoporous BiVO4/AgCl HSMSs have been obtained through solid-phase dual-ion-exchange reactions at 400 degrees C for 2 h. Interestingly, it has been found that Ag+ ions play an indispensable role on the dualion-exchange reactions, and then the BiVO4/AgCl HSMSs are converted into BiVO4/Ag/AgCl ternary HSMSs by a facile visible-light illumination for 2 h. The as-prepared mesoporous BiVO4/Ag/AgCl ternary HSMSs manifest high photocatalytic activity in degrading methyl orange (MO) and phenol under visible-light illumination, and a possible Z-scheme photocatalytic mechanism is proposed to understand the enhanced photochemical properties.