Bipolar properties of model polythiophene derivatives with 1,3,5-triazine units are investigated. The conjugation length is controlled by the meta substitution. In situ spectroelectrochemical UV-Vis-NIR and ESR measurement recorded during electrochemical reduction and oxidation are presented. Spectroelectrochemistry recorded during reduction of polymers in the solid state is especially interesting. Most literature data of spectroelectrochemistry of solid state polymers has been obtained during oxidation which is due to poor stability of radical anions in reduced polymers. Cathodic reduction leads to the formation of stable radical anions in a certain potential range. Exceeding this range leads to overreduction. A similar effect is observed during electrooxidation. Obtained results indicate that not only oligomers with 1,3,5-triazine units but also respective polymers are worth considering during studies on new bipolar polymer materials to broad range of optoelectronic and photovoltaic applications. (C) 2013 Elsevier Ltd. All rights reserved.