Two microporous conjugated polymers with extended phenylene backbones have been synthesized through Suzuki cross-coupling reactions. The structure and the pores of the polymers have been controlled by the use of para- and meta-structure directing 1,3,5-triphenyl tribromide monomers. Gas sorption studies revealed an unprecedented CO2 selectivity over N2 for these conjugated polymer networks. The networks have furthermore been tested as hydrogen storage materials and showed significant hydrogen uptake at high pressures. © 2011 The Royal Society of Chemistry.