Nanometre-sized ZnO crystals doped with Co were synthesized by a co-precipitation method combined with a thermal treatment. By changing the reaction temperature, we can control the crystallite size from roughly 10 nm particles to 20 nm × 200 nm nm rods grown along the hexagonal c-direction. X-ray diffraction and Raman scattering showed growth of high-quality wurtzite ZnO crystals incorporating Co systematically in the ZnO host lattice in the tested range of [Co]<3.0 mol%. Electronic transitions of Co in the oxygen tetrahedron were also observed in optical absorption, giving supporting evidence for systematic substitution of Co into the Zn site.