From the standpoint of chemistry, the metastable nature of nanocrystals provides us plentiful ground for the research of new nanoscale structural transformations. Herein, we report a new phenomenon that trialkylphosphine (TAP) can extract the Ag+ and Bi3+ from their nanostructural chalcogenides and reduce them to the zerovalent state. Based on this principle, a trialkylphosphine-driven chemical transformation route has been developed for the synthesis of a series of metals and metal-sulfide heterostructures with multiple sulfides as the precursors. Using this reaction principle, Ag, Bi, Ag-Ni3S2, Ag-ZnS, Ag-AgInS2, Ag-Bi, and Bi-Cu7S4 nanostructures can be successively synthesized. These Ag- or Bi-based metal chalcogenide heteronanostructures with interesting optical properties or multifunctionalities could be of special interest for a variety of applications, including high-performance catalysis, biological and biomedical sensing, photovoltaic devices, and a new generation of optoelectronic devices.