Uniform Ag nanocubes are reproducibly synthesized by a AgCl particle‐mediated heterogeneous nucleation and disassembly process in polyol chemistry. By introducing N,N‐dimethylformamide (DMF) in a conventional polyol method with HCl etchant, Ag nanocrystals (NCs) begin to be nucleated on the surface of AgCl‐precipitated particles due to the promoted reduction reaction by DMF. The nucleated Ag NCs on the AgCl particles are grown to Ag nanocubes in shape by consuming Ag sources from the AgCl mother particles. Eventually the grown Ag nanocubes are disassembled from the mother AgCl particles because the AgCl particles are fully digested by the growing Ag nanocubes. Density functional theory calculation confirms that the Ag atoms can be favorably deposited on the (100) facet of AgCl particles and the Ag nuclei on the AgCl particles tend to reveal (100) facet.