Depth profiled positronium annihilation lifetime spectroscopy (PALS) has been used to probe the pore characteristics (size, distribution, and interconnectivity) in thin, porous films, including silica, organic and hybrid films. PALS has good sensitivity to and resolution of all pores (both interconnected and closed) in the size range from 0.3 nm to 30 nm, even in films buried under a diffusion barrier. In this technique a focussed beam of several keV positrons forms positronium (Ps, the electron-positron bound state) with a depth distribution that depends on the selected positron beam energy. Ps inherently localizes in the pores where its natural (vacuum) annihilation lifetime of 142 ns is reduced by collisions with the pore surfaces. The collisionally reduced Ps lifetime is correlated with pore size and is the key feature in transforming a Ps lifetime distribution into a pore size distribution. In hybrid films made porous by a degradable porogen PALS readily detects a percolation threshold with increasing porosity that represents the transition from closed pores to interconnected pores. PALS is a non-destructive, depth profiling technique with the only requirement that positrons can be implanted into the porous film where Ps can form.