In the present work, a recently developed statistical theory for adsorption and desorption processes in mesoporous solids, modeled by random Bethe lattices, has been applied to obtain pore size distributions and interpore connectivity from sorption isotherms in real random porous materials, employing a robust and validated methodology. Using the experimental adsorption−desorption N 2 isotherms at 77.4 K on Vycor glass, a porous material with random pore structure, we demonstrate the solution of the inverse problem resulting in extracted pore size distribution and interpore connectivity, notably different from the predictions of earlier theories. The results presented are corroborated by the analysis of 3D digital images of reconstructed Vycor porous glass, showing excellent agreement between the predictions of geometric analysis and the new statistical theory.