A new extended viologen, 4,4'-(2,2'-bithiophene-5,5'-diyl)bis(1-decylpyridinium) triflimide (DTEV2+), has been synthesized and characterized at theoretical and experimental level. Electrochemical and spectro-electrochemical characterization show that this compound undergoes a two-electron reduction mechanism. Density functional computations give insights on the conformational properties of the different reduction species and allow the assignment of the absorption spectra. The agreement between calculated and experimental spectra is quite satisfactory. (c) 2012 Elsevier B.V. All rights reserved.