Contact angle measurements have been widely used to estimate the surface energy of various materials. Such measurements are severely limited with substrate surfaces that exhibit surface restructuring, are contaminated, and/or are porous. Although the captive bubble/drop method addresses the capillarity problem, surface undulations have not previously been accounted for in a quantitative way. We do so here with a series of 8 different pore size synthetic polymer membranes, all fabricated from poly(ether sulfone), as model rough porous surfaces of the same surface chemistry. Also, 3 of the 8 different pore size membranes were rendered hydrophilic through photoinduced graft polymerization producing 17 different modified membranes that are similarly tested. By incorporation of roughness parameters obtained from AFM measurements, corrections to the captive bubble/drop constant angle measurements were successfully made using a simple model of the surface. The predicted average value for the sessile drop contact angle of poly(ether sulfone) accounting for undulations (44.5 +/- 1.3 degrees) was, within error, equal to that value estimated for a smooth relatively nonporous PES nanofiltration membrane (42.9 +/- 2.5 degrees).