Ellipsometric porosimetry (EP) experiments are performed to obtain the adsorption isotherms of water, methanol, and toluene on pristine and damaged SiOCH porous materials. The use of gaseous adsorbates with different polarities, sizes, and surface tensions enables us to probe their affinity with such organosilica surfaces. Using reference t-curves obtained from Statistical Mechanics molecular simulations, we discuss the ability of the MicroPore analysis (MP) method to accurately estimate micropore sizes from EP measurements by comparing them with the mean pore sizes obtained using positron annihilation lifetime spectroscopy (PALS) and grazing incidence small angle X-ray scattering (GISAXS). We also report accessible microporous volumes estimated from the t-plot method used with the reference t-curves obtained by means of molecular simulation. We show that EP characterization of microporous films combined with the MP and t-plot methods can be improved by taking into account the effect of the chemical nature of the pore surface on the variation of the adsorbed thickness (t-curve).