Utilizing self-sacrificed transformation of the dual redox couples Ag/Ag-* and I-/(IO3)(-), we developed a multiplex heterostructure Ag-Agl-AgIO3 by using a simple in-situ reduction strategy and AgIO3 as the sacrificed template. The reaction extent can be easily controlled via adjusting the reductant NaBH4 concentration. Benefiting from both Ag SPR and heterojunctional effects, the photoabsorption in the UV-vis region of Ag-Agl-AgIO3 is monotonously enhanced with increasing reductant concentration. The composite photocatalysts all exhibit highly enhanced photocatalytic activity in degrading methyl orange (MO) under both UV light and visible light irradiation, and Ag-AgI-AgIO3-5 sample shows the optimal photoreactivity, which is 15.2 times that of pure AgIO3. Notably, it also possesses unsurpassed photocatalytic activity against diverse industrial contaminants, pharmaceuticals, and gaseous NO. Besides, Ag-AgI-AgIO3-5 also displays better photocatalytic performance in converting CO2 to CO than AgIO3. Particularly, we explore the reduction products of AgIO3 by other different reductants. It is fascinating that the introduction of sodium citrate, thiourea and hydrazine hydrate results in the products Ag-AgIO3, AgI-AgIO3, Ag-AgI-AgIO3 composites, respectively. This work may not only offer a universally powerful and stable photocatalyst for environmental and energy applications, but also open up a new avenue to develop component-adjustable polynary heterostructural photocatalysts in a facile way. (C) 2016 Elsevier B.V. All rights reserved.