Ultraviolet-ozone (UV-O3) treatment of polyarylene, a semiconductor dielectric polymer, has been characterized using contact angle measurements, x-ray photoelectron spectroscopy, spectroscopic ellipsometry (SE), and ellipsometric porosimetry. Significant modification of the film surface composition is already observed after a short exposure time (30 s). Longer treatment time leads to further increase in oxygen concentration and formation of an oxidized surface layer and densification of the film as evidenced by solvent adsorption data. Results obtained from SE indicate few changes in optical parameters, thickness, and refractive index (RI) of the film, up to 5 min of UV-O3 treatment. Increasing the exposure time further leads to a substantial change in film thickness and an increase in RI. The same trend was observed for porous polyarylene but to a stronger extent. A dense layer at the porous polymer surface is only formed after 20 min of treatment. Under these conditions, the optical properties of the material are strongly modified, with a substantial thickness shrinkage and increase in RI.