Pure rocksalt (c-CoO) and wurtzite (h-CoO) phases of cobaltous oxide (CoO) have been selectively prepared through thermodynamically and kinetically controlled reactions of a single molecular precursor Co(acac)3 (acac: acetylacetonate), respectively. Changing thermal decomposition conditions of the precursor produces different phases and distinct morphologies of the cobaltous oxides. Hexagonal pyramidal shaped h-CoO nanocrystals have been formed by a flash heating of the reaction mixture (185 °C for 2 h, kinetic control condition), whereas cube shaped c-CoO nanocrystals have been produced by a prolonged heating at a relatively low temperature (130 °C for 12 h, thermodynamic control condition). Addition of o-Dichlorobenzene (o-DCB) to the reaction mixture alters the reaction condition to the thermodynamic control regime by slowing down the decomposition rate of the precursor. Further increase of the concentration of o-DCB in the reaction mixture changes the morphology of product from h-CoO hexagonal pyramid...