We review recent progress in studies of the nature of hot electrons generated in metal nanoparticles and thin films on oxide supports and their role in heterogeneous catalysis. We show that the creation of hot electrons and their transport across the metal-oxide interface is an inherent component of energy dissipation accompanying catalytic and photocatalytic surface reactions. The intensity of hot electron flow is well correlated with turnover rates of corresponding reactions. We also show that controlling the flow of hot electrons crossing the interface can lead to the control of chemical reaction rates. Finally, we discuss perspectives of hot-electron-mediated surface chemistry that promise the capability to drive catalytic reactions with enhanced efficiency and selectivity through electron-mediated, non-thermal processes. (C) 2015 Elsevier B.V. All rights reserved.