This paper considers some aspects of the structural behaviour and use of pre-stressed brickwork structures. In its contemporary usage, although brickwork has similar compressive strength properties as concrete, its use in flexurally loaded structural elements has been limited. For practical reasons it is often more difficult to incorporate reinforcement. There are, however, a number of structural forms which are more efficient and easier to construct using pre-stressed brickwork. These include pre-stressed walls and barrel vaults. The paper summarises some key research results which demonstrate that the structural behaviour of pre-stressed brickwork is predictable and comparable with concrete. There are, however, important differences between the two materials. The paper then presents examples of structures for which pre-stressed brickwork has constructional advantages over concrete. The paper concludes that pre-stressed brickwork should not be seen as a direct substitute for concrete but as a material that has considerable benefits when used in appropriate structural forms.