© 2016 Macmillan Publishers Limited, part of Springer Nature. 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 relaxation and rejuvenation induced by thermomechanical processing (that is, elastic and plastic deformation, including cold and hot working, and cyclic loading). The issues that remain to be investigated and the prospects for further progress are discussed.