The redox processes accompanying electrochemical oxidation of 1,3,5-tris(bithiophene)benzene (6TPh) and its products have been investigated using a suite of spectroelectrochemical tools. Investigated trifunctional molecule, featuring reactive bithiophene units can be considered a model of numerous star shaped compounds the building blocks of dense pi-conjugated polymer networks. Accounting for conjugation disruption between the meta-arranged bithiophene groups, it is found that electrochromic films generated upon 6TPh electrooxidation comprise primarily dimers (6TPh)2, whose alpha,omega-diphenylquaterthiophene units are the principal redox doping active species. Upon reaching a certain, electrochemically inconspicuous oxidation threshold, profound changes take place in the oligomer film, incurring irreversible changes to its electroactive properties, previously observed for these systems. An attempt is made to examine the nature of these changes and the impact they have on the doping behaviour of this intriguing pi-conjugated system. (C) 2014 Elsevier B.V. All rights reserved.