The dynamics of frictional motion have been studied for hundreds of years, yet many key aspects of these important processes are not understood. The main challenge in predicting frictional response is the complexity of highly non-equilibrium processes going on in any tribological contact. This includes the continuous detachment and reattachment of multiple microscopic junctions at the sliding interface, the kinetics of which are controlled by the interface temperature. Our experiments reveal a non-monotonic enhancement of dry nanoscale friction at cryogenic temperatures for different material classes. We propose a model that reproduces the experimental observations and shows that the peak in temperature dependence of friction emerges from two competing processes acting at the interface: the thermally activated formation as well as the rupturing of an ensemble of atomic contacts. Our experiments and simulations provide a direct link between the temperature and velocity dependencies of friction, thus offering a new conceptual framework to describe the dynamics of dry nanoscale friction.