ZrO2–8% Y2O3 (YSZ) thick film was deposited on a YSZ–NiO anode and co-sintered to obtain a gas-tight electrolyte for an application as Solid Oxide Fuel Cell. A YSZ sol–gel composite sol is synthesized from a YSZ colloidal binder and a YSZ commercial powder and deposited as a thick (>10 μm) monolayer by the dip-coating process. The evolution of the composite sol viscosity with time and its influence on the deposited film thickness is studied. The influence of the composite sol composition, the film sintering on the films microstructure is also studied in order to achieve dense films. The interest of co-sintering the electrolyte with the anodic support is demonstrated. Ionic conductivity and activation energy are measured on pellets obtained from pressed-powder obtained from (a) the calcination of composite sol and (b) the commercial powder. Conductivity of 0.03 S cm−1 at 800 °C and activation energy of 0.9 eV were measured through impedance spectroscopy. Finally, an entire cell is processed with the developed electrolyte and polarization curves (I–V) were measured at 850 °C. OCV of 1.23 V was achieved, indicating the quality of the synthesized YSZ electrolyte.