The current work introduces the synthesis of inorganic salt nano/micro-crystals during the reduction of hydrogen tetrachloroaurate(III) by Pluronic triblock copolymers (P123, PEO20–PPO70–PEO20). The morphologies and component were confirmed using an electron microscope with an electronic differential system (EDS), and the crystal structures were determined with X-ray diffraction (XRD). The morphologies highly depend on the concentrations of Pluronic and pH values. The mean size of the nanocrystal and hollow micro-crystal were controlled typically in the range of 32–150 nm (side length) and 1.4 μm, respectively. Different from the electrospray–ionization (EI) method, a model in which KCl forms a supersaturated solution in the micellar core of Pluronic is used to explain the formation process. This work provides the new insight that inorganic salt nanocrystals could be synthesized with the template of micelles in pure aqueous solutions.