The knowledge of the thermal evolution of the crystal structure of a cathode material across the usual working conditions in solid oxide fuel cells is essential to understand not only its transport properties but also its chemical and mechanical stability in the working environment. In this regard, high-resolution neutron powder diffraction (NPD) measurements have been performed in air from 25 to 900 degrees C on O-2-treated (350 degrees C/200 bar) La2Ni0.6Cu0.4O4+delta. The crystal structure was Rietveld-refined in the tetragonal F4/mmm space group along all the temperature range. The structural data have been correlated with the transport properties of this layered perovskite. The electrical conductivity Of O-2-treated La2Ni0.6Cu0.4O4+delta exhibits a metal (high T)-to-semiconductor (low T) transition as a function of temperature, displaying a maximum value of 110 S cm(-1) at around 450 degrees C. The largest conductivity corresponds, microscopically, to the shortest axial Ni-O2 distance (2.29(1) angstrom), revealing a major anisotropic component for the electronic transport. We have also performed a durability test at 750 degrees C for 560 h obtaining a very stable value for the electrical conductivity of 87 S cm(-1). The thermal expansion coefficient was 12.8 x 10(-6) K-1 very close to that of the usual SOFC electrolytes. These results exhibit LaNi0.6Cu0.4O4+delta as a possible alternative cathode for IT-SOFC. (c) 2007 Published by Elsevier B.V.