Oxynitride perovskites of early transition metals and rare earth or alkaline earth elements have been reported in the last decade as non-toxic pigments, colossal magnetoresistive materials, high permittivity dielectrics and photocatalysts. Nitride and oxide may occupy the same sites in the perovskite structure, forming solid solutions with ratios that are adjusted by synthesis. The valence states of cations, the bond covalency and the energy of the electronic states can be tuned by the introduction of nitrogen as a consequence of its lower electronegativity, higher electronic polarisability and higher formal anion charge relative to oxygen. This feature article will discuss the influence of the above factors on the crystal chemistry and properties of this group of materials that have emerged as a result of the development of new and controlled synthetic methodologies. © 2012 The Royal Society of Chemistry.