In light of the continuous rise of atmospheric CO₂ concentrations, the utilization of CO₂ has become an important global issue with many barriers such as CO₂ capture, purification, separation, energy requirements for chemical CO₂ fixation, economical considerations and many others. In this work we focus on the catalytic methanol synthesis from CO₂/H₂ mixtures as one of many possibilities for CO₂ utilization. Despite the fact that methanol is produced on industrial scale from syngas (CO/CO₂/H₂) at elevated pressures and temperatures over Cu/ZnO-based catalysts, the reaction mechanism is not well understood. We use periodic, self-consistent density functional theory (DFT) calculations to characterize a large number of well-known and novel surface intermediates on the Cu(111) surface in terms of their binding structures and energetics, and vibrational frequencies. Further, we use the nudged elastic band method to find transitions states for a large number of possible elementary steps occurring during methanol synthesis. The DFT results are subsequently used to derive all necessary parameters in order to develop a comprehensive microkinetic model that allows us to investigate preferred reaction pathways and relevance of surface intermediates and oxygenated byproducts under realistic reaction conditions. The first principles derived parameters for the microkinetic model (enthalpies, entropies, activation barriers, pre-exponential factors) were adjusted to experimental data where necessary. The interplay between theory, experiment and microkineitc modeling of rate data allows for the identification of major routes/intermediates to MeOH synthesis from CO₂ hydrogenation.