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The thermocatalytic hydrogenation of carbon dioxide (CO₂) to methanol is considered as a potential route for green hydrogen storage as well as a mean for utilizing captured CO₂, owing to the many established applications of methanol. Copper–zinc bimetallic catalysts supported on a zirconium-based UiO-66 metal–organic framework (MOF) were prepared via slurry phase impregnation and benchmarked against the promoted, co-precipitated, conventional ternary CuO/ZnO/Al₂O₃ (CZA) catalyst for the thermocatalytic hydrogenation of CO₂ to methanol. A decrease in crystallinity and specific surface area of the UiO-66 support was observed using X-ray diffraction and N₂-sorption isotherms, whereas hydrogen-temperature-programmed reduction and X-ray photoelectron spectroscopy revealed the presence of copper active sites after impregnation and thermal activation. Other characterisation techniques such as scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis were employed to assess the physicochemical properties of the resulting catalysts. The UiO-66 (Zr) MOF-supported catalyst exhibited a good CO₂ conversion of 27 and 16% selectivity towards methanol, whereas the magnesium-promoted CZA catalyst had a CO₂ conversion of 31% and methanol selectivity of 24%. The prepared catalysts performed similarly to a CZA commercial catalyst which exhibited a CO₂ conversion and methanol selectivity of 30 and 15%. The study demonstrates the prospective use of Cu-Zn bimetallic catalysts supported on MOFs for direct CO₂ hydrogenation to produce green methanol.