top In this paper we report the successful incorporation of silicon into Sr1−yCayMnO3−δ perovskite materials for potential applications in cathodes for solid oxide fuel cells. The Si substitution onto the B site of a 29Si enriched Sr1−yCayMn1−xSixO3−δ perovskite system is confirmed by 29Si MAS NMR measurements at low B0 field. The very large paramagnetic shift ([similar]3000–3500 ppm) and anisotropy (span [similar]4000 ppm) suggests that the Si4+ species experiences both Fermi contact and electron-nuclear dipolar contributions to the paramagnetic interaction with the Mn3+/4+ centres. An improvement in the conductivity is observed for low level Si doping, which can be attributed to two factors. The first of these is attributed to the tetrahedral coordination preference of Si leading to the introduction of oxide ion vacancies, and hence a partial reduction of Mn4+ to give mixed valence Mn. Secondly, for samples with high Sr levels, the undoped systems adopt a hexagonal perovskite structure containing face sharing of MnO6 octahedra, while Si doping is shown to help to stabilise the more highly conducting cubic perovskite containing corner linked octahedra. The level of Si, x, required to stabilise the cubic Sr1−yCayMn1−xSixO3−δ perovskite in these cases is shown to decrease with increasing Ca content; thus cubic symmetry is achieved at x = 0.05 for the Sr0.5Ca0.5Mn1−xSixO3−δ series; x = 0.075 for Sr0.7Ca0.3Mn1−xSixO3−δ; x = 0.10 for Sr0.8Ca0.2Mn1−xSixO3−δ; and x = 0.15 for SrMn1−xSixO3−δ. Composites with 50% Ce0.9Gd0.1O1.95 were examined on dense Ce0.9Gd0.1O1.95 pellets. For all series an improvement in the area specific resistances (ASR) values is observed for the Si-doped samples. Thus these preliminary results show that silicon can be incorporated into perovskite cathode materials and can have a beneficial effect on the performance.