The growth of strongly oriented or epitaxial thin films of metal oxides generally requires relatively high growth temperatures or infusion of energy to the growth surface through means such as ion bombardment. We have grown high quality epitaxial thin films of Co₃O₄ on different substrates at a temperature as low as 400°C by low-pressure metalorganic chemical vapour deposition (MOCVD) using cobalt(II) acetylacetonate as the precursor. With oxygen as the reactant gas, polycrystalline Co₃O₄ films are formed on glass and Si (1 0 0) in the temperature range 400–550°C. Under similar conditions of growth, highly oriented films of Co₃O₄ are formed on SrTiO₃ (1 0 0) and LaAlO₃ (1 0 0). The activation energy for the growth of polycrystalline films on glass is significantly higher than that for epitaxial growth on SrTiO₃ (1 0 0). The film on LaAlO₃ (1 0 0) grown at 450°C shows a rocking curve FWHM of 1.61°, which reduces to 1.32° when it is annealed in oxygen at 725°C. The film on SrTiO₃ (1 0 0) has a FWHM of 0.33° (as deposited) and 0.29° (after annealing at 725°C). The φ-scan analysis shows cube-on–cube epitaxy on both these substrates. The quality of epitaxy on SrTiO₃ (1 0 0) is comparable to the best of the perovskite-based oxide thin films grown at significantly higher temperatures. A plausible mechanism is proposed for the observed low temperature epitaxy.