In this work, we report the potential of sol–gel process to prepare cathode and electrolyte thin and thick layers on anodic NiO-YSZ supports which were also made from powders prepared by sol–gel route. YSZ and La2 − xNiO4 + δ, La4Ni3O10 were synthesized as electrolyte and cathode materials for SOFC applications. For electrolyte shaping, yttria stabilized zirconia (YSZ, 8% Y2O3) thick films were cast onto porous NiO-YSZ composite substrates by a dip-coating process using a new suspension formulation. Part of the YSZ precursor colloidal sol was added in the suspension to ensure both homogeneity and adhesion of the electrolyte on the anodic substrate after thermal treatment at 1400 °C for 2 h. By precisely controlling the synthesis parameters, dense and gas-tight layers with thicknesses in the range of 10–20 μm have been obtained. Gas-tightness was confirmed by He permeation measurements. Concerning cathode processing, a duplex microstructured cathode consisting of both La2 − xNiO4 + δ ultra-thin films (few nanometers) and La2 − xNiO4 + δ and/or La4Ni3O10 thick layers (few micrometers) was prepared on YSZ substrates by the dip-coating process, with the thickness being dependent on the nature of the dip-coated solution (polymeric sol or adequate suspension). The derived cathode microstructure, related to the number/thickness of layers and type of architecture, was correlated to the good cell electrochemical performances. Concerning cathode processing, a duplex microstructured cathode consisting of both La2 ? xNiO4 + ? ultra-thin films (few nanometers) and La2 ? xNiO4 + ? and/or La4Ni3O10 thick layers (few micrometers) was prepared on YSZ substrates by the dip-coating process, with the thickness being dependent on the nature of the dip-coated solution (polymeric sol or adequate suspension). The derived cathode microstructure, related to the number/thickness of layers and type of architecture, was correlated to the good cell electrochemical performances.