Four thiophene-based monomers have been synthesized by Stine- or Suzuki-type couplings followed by chemical or electrochemical polymerization into microporous polymer networks (MPNs) with high BET surface areas (S-BET). Similar S-BET values of up to 2020 and 2135 m(2) g(-1) have been determined for tetraphenylmethane-cored bulk MPN powders and thin films, respectively. Electrochemical polymerization in boron trifluoride diethyl etherate (BFEE)/dichloromethane (DCM) mixtures allows for the generation of MEN films with optimized porosity. Moreover, an interesting effect of boron trifluoride on the connectivity of the monomeric units during electropolymerization is observed for 3-thienyl-based monomers. Finally, the electrochemical reduction of 1,3,5-trinitrobenzene at MEN-modified glassy carbon (GC) electrodes shows increased cathodic responses compared to nonmodified GC electrodes due to interaction between electron-deficient nitroaromatic analyte and electron-rich MEN film. The influence of the specific surface area of MPNs on the electrochemical response is also studied for this class of materials.