This paper describes a powerful and facile synthesis of CdSe hollow nanostructures via a sacrificial template method employing the Kirkendall diffusion effect for void formation and an anion exchange reaction for selenization. The CdSe hollow nanowires and nanoparticles were easily transformed from a sacrificial template of CdO nanowires that were formed by thermal Ostwald ripening. The distinctive structures of CdO sacrificial templates were developed through thermodynamically spontaneous process. The morphology of each CdSe nanostructure could be controlled by one of each CdO sacrificial template which was calcined at several different temperatures. Their microstructure was analyzed by field-emission scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, and their optical properties were compared using light absorption. The suggested process for synthesis of hollow nanostructures could also be applied to the formation of other hollow chalcogenide compounds.