Recently LaNi1−xFexO3 materials have been suggested as good candidates for cathodes for Intermediate Temperature Solid Oxide Fuel Cells. The electrical conductivity and the morphology of LaNi0.6Fe0.4O3 samples have been studied as a function of preparation route and calcination temperature. The conductivity, mainly electronic, strongly depends on the densification of the material, which is influenced by the preparation procedure. DFT calculations indicate that the conduction bands of LaNi0.6Fe0.4O3 are mainly made up of Fe and Ni 3d states and that there is a small bandwidth (2.3 eV) around the Fermi level. Moreover, a small polaron mechanism for the electronic conduction in this material is suggested by the simulations.