In this paper, tricobalt tetraoxide (Co3O4) catalyst was coated on the polydimethylsiloxane microchannel by the plasma-enhanced metal-organic chemical vapor deposition technology. The obtained Co3O4 film was characterized by SEM, XRD, XPS, and TEM, and the results show that the as-deposited Co3O4 film was initially composed of many cauliflowers-shaped microclusters. Also, the microcauliflower was transformed from an amorphous phase to a crystal phase when the Co3O4 film was treated by Ar and O2 plasma for more than 20 min, and the crystal lattice line occurred on the surface of nano-sized-Co3O4 particles. Meanwhile, the interface of Co3O4 particles with diameter between 3 and 12 nm became obvious and some nano-catkin structures were also formed on the Co3O4 film. The ratio of Co3+/Co2+ in the spinel-type Co3O4 was nearly 2, and the nano-particles predominantly expose their {311}, {111}, and {220} planes. These morphologies and structure characteristics were found to be ideal for increasing the catalytic activity efficiency of Co3O4 for CO oxidation, and the catalytic stability of Co3O4 coated on the organic microreactor lasted nearly 85 h for trace CO oxidation at room temperature.