Triangular Ag nanoprisms are a type of most-studied noble-metal nanostructures over the past decade owing to their special structural architecture and outstanding optical and catalytic properties for a wide range of applications. Nevertheless, in contrast to active research for the synthesis of phase-pure Ag nanoprisms, no asymmetric heterodimers containing Ag prisms have been developed so far, probably due to lack of suitable synthetic methods. Herein, we devise a simple ion-exchange method to synthesize Ag2S/Ag heterodimers at room temperature, through which Ag nanoprisms with controllable size and thickness can be fabricated. Formation chemistry and optical properties of the heterodimers have been investigated. These semiconductor/metal heterodimers have exhibited remarkable bactericidal activity to E. coli cells under visible light illumination.