The synthesis of extremely small mesoporous silica nanoparticles via a specific co-condensation process with phenyl groups is demonstrated. The suspensions are ideally suited for the production of nanoscale thin films by spin-coating. Thanks to the small particle size and the resulting low surface roughness, the films show excellent optical qualities and exhibit good diffusion properties and a highly accessible pore system. The availability of such homogeneous porous thin films made it possible to use ellipsometric porosimetry (EP) as a convenient method to determine the effective porosity of the films on their original support without destroying it. It was possible to record sorption isotherms of the thin films with ellipsometry and to correlate the data with nitrogen sorption data of dried powders of the same material. The thin films showed very low refractive indices of around 1.2.