Abstract An efficient and environment-friendly process, consisting of acid-catalyzed sol-gel process combined with evaporation induced self-assembly, was conducted to build antireflective (AR) layer stacks for concentrated solar applications. Considering the external factors that may alter the optical properties of the system when operating outdoors, such as soiling, harsh climate conditions and alkali ions diffusion from glass, several stack configurations were proposed. Particularly, the effect of a methyl-silylating post-treatment, the presence of the inner layer and the optimization of sintering temperature have been devised in order to minimize soiling adherence and alkali diffusion from the glass substrate and to assure the required robustness to comply with the durability requirements. The assessment consisted of (i) an analysis of the optical transmittance, reflectance and refractive index and (ii) hydrophobicity and effect of water absorption on the external porous coatings in relation to the results of accelerated aging tests following photovoltaics standards. The main goal was to achieve the most rational design, based on a proper trade-off between cost efficiency, processability, optical properties and reliability during real life operation.