A facile method of fabrication of ceramic monoliths assisted by 3D printing was developed for preparation of Co3O4-based catalysts of total oxidation of volatile organic compounds. The proposed approach was based on the production of a resin template, which was subsequently used at a casting step for the construction of corundum monolith. The walls of this material were additionally coated with a MFI zeolite layer providing the possibility of modification with a Co3O4 precursor using ion-exchange and impregnation techniques. The parent and Co3O4-modified monoliths with varying active phase content were characterized by SEM/EDS, XRD, XRF, XPS, UV-visDR and H-2-TPR. Their catalytic performance in the toluene combustion was also tested. It was shown that the formation of Co3O4 spinel particles highly dispersed on the zeolite-coated monolith resulted in excellent catalytic activity measured by very high TOF values. Furthermore, stability tests confirmed that the obtained monolith catalysts can work for prolonged reaction time without noticeable changes in the toluene conversion and selectivity to CO2.