Microporous poly(tri(4-ethynylphenyl)amine) networks were synthesized by palladium-catalyzed Sonogashira-Hagihara cross-coupling chemistry with apparent Brunauer-Emmet-Teller (BET) specific surface areas in the range 500-1100 m(2)/g. It was found that very fine synthetic control over physical properties such as BET surface area, Langmuir surface area, micropore surface area, micropore volume, and bulk density could be achieved by varying the average monomer strut length. The micropore structure and micropore surface area were rationalized by atomistic simulations for one network, NCMP-0, based on multiple physical characterization data.