The morphological manipulation, structural characterization, and photoluminescence properties of different CdSe nanocrystals are reported. Several different CdSe structures, including nanowires, nanorods, nanoparticles, and tetrapod crystals, have been grown on silicon substrates by means of simple, Si-assisted chemical vapor deposition. By manipulating the growth driving force (i.e., the degree of supersaturation), the morphology of the CdSe nanocrystals can be varied sequentially from nanowires/nanorods to nanoparticles to tetrapod structures. The optical properties of the CdSe nanocrystals are investigated using photoluminescence spectroscopy. Some thermodynamic models are proposed to explain the results.