CoO and Co nanocrystals with cubic crystal structures were prepared by thermal decomposition of cobalt(II) acetate tetrahydrate in a mixture of oleylamine and oleic acid under the protection of nitrogen gas at 300 °C for 2 h. The products of CoO or Co nanocrystals are determined by the relative amount of oleylamine due to its reducibility. The sizes and shapes of CoO or Co can be controlled by the ratio of cobalt : oleylamine : oleic acid due to different binding capabilities of the two capping ligands (oleylamine and oleic acid). A modification of the surface state by surface passivation arising from the capping ligands for CoO nanocrystals leads to the blue shift of the ligand–metal charge transfer (LMCT) absorption. Room temperature ferromagnetism originating from uncompensated surface spins, as well as magnetic moments weakly exchange coupled to the CoO lattice due to defects inside CoO nanoparticles, are observed. The magnetic behaviors of CoO and Co nanoparticles also shed light on the synthesis and the magnetic properties of the antiferromagnetic and ferromagnetic nanomaterials.