Metal-doped (Mn, Cu, Ni, and Fe) cobalt oxides were prepared by a coprecipitation method and were used as catalysts for the total oxidation of toluene and propane. The metal-doped catalysts displayed the same cubic spinel Co3O4 structure as the pure cobalt oxide did; the variation of cell parameter demonstrated the incorporation of dopants into the cobalt oxide lattice. FTIR spectra revealed the segregation of manganese oxide and iron oxide. The addition of dopant greatly influenced the crystallite size, strain, specific surface area, reducibility, and subsequently the catalytic performance of cobalt oxides. The catalytic activity of new materials was closely related to the nature of the dopant and the type of hydrocarbons. The doping of Mn, Ni, and Cu favored the combustion of toluene, with the Mn-doped one being the most active (14.6 × 10−8 mol gCo−1 s−1 at 210 °C; T50 = 224 °C), while the presence of Fe in Co3O4 inhibited its toluene activity. Regarding the combustion of propane, the introduction of Cu, Ni, and Fe had a negative effect on propane oxidation, while the presence of Mn in Co3O4 maintained its propane activity (6.1 × 10−8 mol gCo−1 s−1 at 160 °C; T50 = 201 °C). The excellent performance of Mn-doped Co3O4 could be attributed to the small grain size, high degree of strain, high surface area, and strong interaction between Mn and Co. Moreover, the presence of 4.4 vol.% H2O badly suppressed the activity of metal-doped catalysts for propane oxidation, among them, Fe-doped Co3O4 showed the best durability for wet propane combustion.