The CEA/DAM megajoule-class pulsed Nd:glass laser devoted to Inertial Confinement Fusion (ICF) research will require 240 cavity-end mirrors. The approved laser design necessitates 42-cm x 46-cm x 9-cm highly-reflective (HR)-coated substrates representing more than 50 m(2) of coated area. Prototypes of these dielectric mirrors were prepared with interference quaterwave stacks of SiO2 and ZrO2-PVP (PolyVinylPyrrolidone) thin films starting from sol-gel colloidal suspensions (sols). Low refractive index material was based on nanosized silica particles and high refractive index coating solution was made of a composite system. The colloidal/polymeric ratio in the composite system has been optimized regarding refractive index value, laser damage threshold and chemical interactions have been studied using FT-IR spectroscopy. A deposition technique so-called "Laminar Flow Coating" (LFC) has been associated to sol-gel chemistry for HR laser damage-resistant sol-gel coating development. This novel coating method confirmed its main advantages compared to dipping or spinning processes: coating large flat square substrates at room temperature with small solution consumption, good thickness uniformity, weak edge-effects, induced stress-free coating, good optical properties and laser damage resistance fulfilling.