Herein we report a series of porous organic polymers (POPs) synthesized through a Sonogashira cross-coupling reaction containing hexaphenylbenzene (HEX) and hexabenzocoronene (HBC) with varying peripheral substitution. We observed vastly different gas sorption properties depending on substituent size and the extent of conjugation in the monomer core structure with BET surface areas ranging from 320 m(2)/g for HBC-POP-4 to 1140 m(2)/g for HEX-POP-3. In order to more clearly understand the effects of functional group substitution on the properties of these materials, we have characterized these POPs using N-2, CO2, and H-2 sorption measurements, powder X-ray diffraction, FT-IR spectroscopy, TGA, and EDX.