In this work, a 3D printing methodology based on the robocasting of catalytic ink pastes was applied to obtain structured matrix-like cylinders as innovative materials for an effective utilization of carbon dioxide. The influence of three different binders (i.e., PEI, HPMC and MC) on the physio-chemical, mechanical and catalytic properties of multi-channel monoliths was studied against a reference binder-free powdered system in order to envisage the effectiveness of the printing procedure in realizing hybrid advanced materials at a higher control and reproducibility than from traditional preparation techniques. In terms of textural and structural properties, the micro-extruded 3D cylinders only evidenced a slight difference in terms of relative crystallinity, with minor effects on the surface area exposure in relation to the specific binder used during the direct ink writing process. More importantly, the typology of binder significantly affected the rheological properties of the catalytic ink, with the need of a controlled viscosity to ensure a suitable thixotropic behaviour of the extrudable pastes, finally determining an optimal mechanical resistance of the final 3D monolith. The experimental validation of the hybrid multi-channel cylinders under conditions of CO2 hydrogenation demonstrated the great potential of additive manufacturing in the realization of catalyst architectures characterized by unique features and fidelity scarcely reproducible via conventional synthetic techniques.