ABSTRACTPositron annihilation lifetime spectroscopy (PALS) is a common technique used to characterize the porosity of polymers. Here, we expand its use to the study of ordered nanoporous polymer monoliths. Polystyrene (PS) monoliths with aligned cylindrical pores ranging in diameters from 15 to 35 nm were examined. Such large pores push the boundaries of the PALS technique. To achieve robust measurement, our system used larger detectors than those typically used for monolithic polymer samples. This was done to improve data rates while sacrificing timing resolution. Pore sizes determined using PALS were consistent with measurements made using small angle x‐ray scattering. In addition, PALS was able to detect the collapse of the pores when the monolithic sample was heated above theTgof PS. Because PALS measurements are not sensitive to the nature of the order within the structure nor are they, sensitive to the open or closed nature of the pores this technique could be expanded to a variety of other sample types. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1157–1161