Catalytic reactions that enable the formation of new bonds to carbon centres play a pervasive role in the state-of-the-art synthesis of organic molecules and macromolecules. In contrast, the development of analogous processes as routes to main group compounds and materials has been much slower. Nevertheless, recent advances have led to a broad expansion of this field and now allow access to a wide range of catenated structures based on elements across the p block. These breakthroughs have already impacted areas such as hydrogen storage and transfer, functional inorganic polymers and ceramic thin films. Dehydrogenation and dehydrocoupling processes are particularly well developed and may be mediated by either transition metal or main group catalysts. Such pathways represent an increasingly attractive and convenient alternative to traditional routes, such as salt metathesis and reductive coupling reactions. An overview of this emerging area is presented in this Review with a focus on recent developments and future challenges.