Transforming nanostructures into hollow ones represents a unique synthetic strategy for achieving new properties that do not exist in their solid counterparts, boosting applications in a broader range. The chemical nature of the reactive nanostructures (or sacrificial template nanostructures) determines the reaction kinetics of hollowing them along with the transformation of chemical compositions, which influences the controllability of synthesis. For example, uniform silver chlorobromide nanocubes can be used a class of sacrificial template nanostructures to regulate and maintain an extremely low concentration of available Ag+ that reacts with different thiol molecules to form silver thiolate with high controllability over the reaction kinetics. Such kinetic controllability enables the transformation of the silver chlorobromide nanocubes to hollow nanocages of silver thiolate. In contrast, the direct reaction of Ag+ ions with thiol molecules forms silver thiolate particles with irregular sizes and geometries. Moreover, the sacrificial silver chlorobromide nanocubes expose their surfaces to provide the heterogeneous nucleation sites for condensation of silver thiolate, further improving the controllability to benefit their transformation into hollow nanocages. Due to the improved controllability over reaction kinetics, the process of hollowing silver chlorobromide nanocubes can be terminated at any desired stage to form silver thiolate nanocages with the appropriate wall thickness. Time-dependent electron microscopic, X-ray diffraction, and UV-visible spectrometric studies reveal detailed insights into the structural evolution of crystals in terms of amount and dimensions during the hollowing transformation. This method represents scalable and versatile strategy to control the kinetics of fast reactions involved in the synthesis of colloidal nanoparticles, thus enabling the synthesis of uniform nanocages with desirable parameters. The availability of various silver-based hollow nanostructures provides the opportunity to explore potential interesting properties with real-world applications such as in electrocatalysis and photocatalysis.