Understanding gas-surface reaction dynamics, such as the rupture and formation of bonds in vibrationally and translationally excited ('hot') molecules, is important to provide mechanistic insight into heterogeneous catalytic processes. Although it has been established that such excitation can affect the reactions occurring via dissociative mechanisms, for associative mechanisms-in which the gas-phase reactant collides directly with a surface-adsorbed species-only translational excitation has been observed to affect reactivity. Here we report a bond-formation reaction that is driven by the vibrational energy of reactant molecules and occurs via an (associative) Eley-Rideal-type mechanism, in which the reaction takes place in a single collision. Hot CO2 in a molecular beam is found to react with pre-adsorbed hydrogen atoms directly on cold Cu(111) and Cu(100) surfaces to form formate adspecies. The vibrational energy of CO2 is more effective at promoting the reaction than translational energy, the reaction rate is independent of the surface temperature and the experimental results are consistent with density functional theory calculations.