Two types of microporous polymeric networks have been prepared from monomers containing N-tert-butoxycarbonyl-protected pyrrole by FeCl3-mediated oxidative coupling polymerization. These materials were predominantly microporous (with BET surface areas of 828 m(2) g(-1) and 1408 m(2) g(-1)), exhibiting high CO2 uptake capacities (1.96 mmol g(-1) and 2.69 mmol g(-1) at 273 K, 1 bar). Novel microporous polymeric films (with BET surface areas of 570 m(2) g(-1) and 593 m(2) g(-1)) were fabricated through in situ polymerization of monomers on a flat glass dish using a sol gel process catalyzed by trifluoroacetic acid. (C) 2013 Elsevier Ltd. All rights reserved.