A novel organometallic synthetic method has been developed for the preparation of crystalline ZnO nanoparticles of controlled size and shape. Isotropic nanoparticles with a mean size between 3 and 6 nm and nanorods with a mean diameter of 3–4 nm and length up to 120 nm have been obtained in this way. This synthetic method takes advantage of the exothermic reaction of the precursor Zn(c-C6H11)2 (1) toward moisture and air and involves the presence of long-alkyl-chain amines as stabilizing ligands. The influence of the different experimental parameters (concentration, solvent, nature of the ligand, time, and temperature) on the size and shape of the ZnO nanoparticles has been studied, together with the mechanism of their formation, by NMR spectroscopy, transmission electron microscopy, and X-ray diffraction techniques. The nanoparticles prepared in this way can be dissolved in most of the common organic solvents, forming colloidal solutions. The surface state of the nanoparticles as well as the possibility of forming luminescent solutions from which regular monolayers can be deposited are also reported.