Ni-NiO 30% electrodes coated with LiMg0.05Co0.95O2 cobaltite deposited on the substrate by complex sol-gel process were investigated by neutron diffraction. The measurements were carried out at the D20 diffractometer at the High Flux Reactor of the Institut Max von Laue – Paul Langevin. As the catalytic layer is only a few microns thick, the diffracting volume of the cobaltite phase was optimised by stacking small rectangular pieces cut from the original electrode and assuming that the catalytic layer on the electrodes was homogenous. A pure cobaltite sample was used as a reference for identifying in the complete electrode the diffraction peaks of the catalytic layer. Both an as-received sample and an electrode tested for 100 h at 650 °C in a cell were measured. Despite the small diffracting volume, due to the high flux available at D20, it was possible to detect the hexagonal phase of the catalytic layer and estimate its volume fraction in the as-received sample; in the tested electrode the original crystallographic structure is completely modified but information on the phases present can be obtained.