Co3O4 catalysts were prepared via carbonate precipitation and subsequent calcination under specific conditions. The different catalysts were characterized as received using several techniques and tested in the total oxidation of toluene or propane. Calcination at low temperature or under dynamic conditions resulted in Co3O4 catalysts with small crystallite sizes and large surface areas. The performances of the Co3O4 catalysts appeared to be closely related to the low-temperature reducibility. The best catalyst, Co-350D, showed a toluene oxidation rate of 44.5 nmol g−1 s−1 at 200 °C and a propane oxidation rate of 54.0 nmol g−1 s−1 at 150 °C. Meanwhile, Co-350D exhibited excellent cycling stability and decent long-term durability in both reactions.