Semiconductor optical fibre technologies have grown rapidly in the last decade and there are now a range of production and post-processing techniques that allow for a vast degree of control over the core material's optoelectronic properties. These methodologies and the unique optical fibre geometry provide an exciting platform for materials engineering and fibres can now be produced with single crystal cores, low optical losses, tunable strain, and inscribable phase composition. This review discusses the state-of-the-art regarding the production of silicon optical fibres in amorphous and crystalline form and then looks at the post-processing techniques and the improved material quality and new functionality that they afford.