Cu/ZnO/Al2O3 catalysts used to synthesize methanol undergo extensive deactivation during use, mainly due to sintering. Here, we report on formulations wherein deactivation has been substantially reduced by the targeted use of a small quantity of a Si-based promoter, resulting in accrued activity benefits that can exceed a factor of 1.8 versus unpromoted catalysts. This enhanced stability also provides longer lifetimes, up to double that of prior generation catalysts. Detailed characterization of a library of aged catalysts has allowed the most important deactivation mechanisms to be established and the chemical state of the silicon promoter to be identified. We show that silicon is incorporated within the ZnO lattice, providing a pronounced improvement in the hydrothermal stability of this component. These findings have important implications for sustainable methanol production from H2 and CO2.