In this work, three Co3O4 nanostructures with different morphologies (cubes, rods, and sheets) were synthesized using a hydrothermal method and tested for the CO2 hydrogenation reaction. The physicochemical properties of the structured Co3O4 were well characterized by X-ray diffraction (XRD), Raman spectroscopy, field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), hydrogen temperature-programmed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) techniques. Based on the characterization, cube, rod, and sheet Co3O4 nanostructures were found to expose the (100), (110), and (112) planes, respectively. The effect of cobalt oxide morphologies with different exposed surfaces on the activity and selectivity toward CO2 hydrogenation reaction in a plug-flow reactor operated between 200 and 400 °C under atmospheric pressure conditions was explored. The results establish a correlation of the catalytic activity with morphological structures in the order rods > sheets > cubes. H2-TPR and XPS studies demonstrated that the high reducibility of Co3O4 rod makes it an excellent catalyst for CO2 hydrogenation. © 2023 American Chemical Society.