Au nanostructures attract much attention due to their potential applications in many fields. The controlled synthesis is critical to their properties modulation and applications. AgNO3-assisted synthesis is a widely used method for controllably preparing Au nanostructures in aqueous system. Herein, the effect of AgNO3 on the growth of Au nanostructures in polyol is studied. We observe an unusual effect that AgNO3 can induce the formation of pentatwinned Au nanostructures (nanorods and decahedra) and block the growth of Au nanorods. More interestingly, this blocking effect can be tuned through controlling the amount of AgNO3. A moderate amount of AgNO3 facilitates the formation of Au nanorods. A large amount of AgNO3 completely blocks the growth of nanorods and favors the formation of high quality decahedra (decahedra can be considered as nanorods with 0 nm longitudinal length). Besides, this blocking effect also allows preparation of different high-index-faceted Au nanobipyramids. These prepared Au nanostructures further serve as starting templates to fabricate other heterostructured Au/Ag nanomaterials, such as Ag-Au-Ag segmental nanorods, Au@Ag core-shelled nanostructures. The prepared nanostructures exhibit size- and structure-dependent catalytic performance in the reduction of p-nitrophenol to p-aminophenol by sodium borohydride.