A new series of heteroleptic complexes of cobalt were synthesized using aminoalkoxide and β-diketonate ligands. The complexes, [Co(dmamp)(acac)]2 (3), [Co(dmamp)(tfac)]2 (4), [Co(dmamp)(hfac)]2 (5), [Co(dmamp)(tmhd)]2 (6), and [Co(dmamb)(tmhd)]2 (7), were prepared by two-step substitution reactions and studied using Fourier transform infrared spectroscopy, mass spectrometry, elemental analysis, and thermogravimetric analysis (TGA). Complexes 3-7 displayed dimeric molecular structures for all of the complexes with cobalt metal centers interconnected by μ2-O bonding by the alkoxy oxygen atom. TGA and a thermal study of the complexes displayed high volatilities and stabilities for complexes 6 and 7, with sublimation temperatures of 120 °C/0.5 Torr and 130 °C/0.5 Torr, respectively.