The present work reports the synthesis, structure and electrochemical assessment of Cu-doped calcium cobaltites as cathode materials for solid oxide fuel cells (SOFCs). Powders of composition Ca3-xCuxCo4O9-delta (0 <= x <= 0.2) were obtained by a proteic sol-gel method which uses gelatin as polymerizing agent. As-prepared materials were calcined at 900 degrees C for 1 h and characterized by X-ray diffraction, with Rietveld refinement of the diffraction data, and scanning electron microscopy. Screen printed porous electrodes fired (at 950 degrees C for 2 h) on both faces of ceria based electrolytes were electrochemically characterized by impedance spectroscopy between 600 and 800 degrees C in air atmosphere. The results indicated the attainment of Ca3-xCuxCo4O9-delta solid solutions with monoclinic misfit layered structure and around 2 vol% Co3O4 as a secondary phase. Micro-plates like powders had irregular shape and average diameter near 2 mu m. The area specific resistance (ASR) is in line with literature data for cathodes of similar compositions prepared by other synthetic routes. ASR was optimized for the composition Ca2.99Cu0.01Co4O9-delta, achieving 0.84 Omega cm(2) at 800 degrees C in air. (C) 2016 Elsevier B.V. All rights reserved.