The two reactions take place simultaneously through a solidphase ion-exchange process which is hard to achieve at a low temperature in solution. Very interestingly, it has been found that Ag+ ions play an indispensable role on the dual-ionexchange reactions. In step II, ternary products of BiVO4/Ag/ AgCl ternary HSMSs are fabricated from the BiVO4/AgCl binary HSMSs through a simple visible-light induced reduction process for 2 h. As expected, the as-prepared mesoporous BiVO4/Ag/AgCl ternary HSMSs manifest high photocatalytic activity in degrading methyl orange (MO) and colorless organic phenol under visible-light illumination. In addition, a possible Z-scheme photocatalytic mechanism is proposed to understand the enhanced photochemical properties.