Templating is one of the most popular methods for generating nanocomposite and nanoporous films and the resultant pore size and pore interconnection length depend strongly on porogen concentration/porosity among other factors. Positronium Annihilation Lifetime Spectroscopy (PALS) analysis has been performed on a series of films produced using increasing concentrations of a type of cyclodextrin (CD) porogen in a modified silsesquioxane host matrix. PALS reveals the relationship between the resulting pore structure (both size and interconnection length) and porosity, which can be used to deduce pore shape. At low porogen concentration, isolated pores are resolved, but the pore size is consistent with a cluster of two or three CD molecules, rather than an individual one. As the porosity increases, the aggregation of the porogen domains appears to be more 3-dimensional (pseudo-random) with gradual increase in pore size. Computer simulations using a random pore growth model show consistent trends for pore size growth, but the agreement is poor for interconnection length. It is a key demonstration of the usefulness of PALS in untangling the fundamental pore structure and its evolution in porosity. PALS characterization of porosity provides novel feedback in the understanding and design of nanoporous materials.