The perovskites (La0.85Sr0.15)0.98CoO3 − λ and (La0.85Sr0.15)1.00CoO3 − λ have been investigated using x-ray diffraction (XRD), scanning electron microscopy (SEM) and electrical conductivity relaxation (ECR). This system was chosen in order to investigate the influence of cation vacancies on the transport properties in the materials. From ECR-measurements it is concluded that no difference in the chemical diffusion coefficient for oxide ions between the two samples can be found. The activation energy for the chemical diffusion coefficient has been found to be 107 ± 5 kJ mol−1. However, the surface exchange coefficient differs between the two samples. The Co-rich sample has a significantly higher surface exchange coefficient than the A/B-stoichiometric sample. For both samples the surface exchange coefficient was almost independent of the temperature. At all temperatures the Co-rich sample had a significantly higher electrical conductivity. The difference in electrical conductivity between the two samples diminished when going to higher temperatures. Both materials can be assigned to a single phase hexagonal perovskite. An annealed sample of (La0.85Sr0.15)0.98CoO3 − λ did however contain an unidentified secondary phase on the surface.