A heating treatment strategy for inducing size and shape change of composite nanoparticles in solutions is described. The composite nanoparticles are similar to 2 nn gold cores encapsulated with alkanethiolate monolayers. The development of abilities in size and shape controls constitutes the motivation of this work. We demonstrated a remarkable evolution of the preformed particles in solutions toward monodispersed larger core sizes with well-defined and highly faceted morphologies. The particles thus evolved were encapsulated with the thiolate shells, and exhibited striking propensities of forming long-range ordered arrays. The morphological and structural evolutions were characterized using transmission electron microscopy, X-ray diffraction, UV-vis and infrared spectroscopies. Although temperature-driven crystal growth is known for nonencapsulated particles, the evolution of the thiolate-encapsulated nanoparticles in solutions into well-defined morphologies represents an intriguing example of temperature manipulations in size monodispersity and shape control.