| For crystalline metals the science, technology, and application of thermomechanical processing are established, but this is not true for glasses. Metallic glasses-because they can be plastically deformed-offer a unique opportunity to study the effects of thermomechanical treatments on the structure and properties of glasses. Depending on the rate of cooling, various glassy states can form from a liquid. Slower cooling gives states of lower enthalpy and smaller volume; such states might also be reached by annealing, which induces structural 'relaxation'. A reduction in the degree of relaxation, or 'rejuvenation', is achievable through processes such as irradiation and mechanical deformation. In this Review, we explore the extent of