Novel hexyl-substituted bisthiophene compounds containing a thiazolothiazole(5,4-d) unit have been explored. The molecules are soluble in common organic solvents, which would enhance their chance of possible integration in printable electronics. Synthesis and complete elucidation of the chemical structures by detailed 1D/2D NMR spectroscopy are described. This provides interesting input for chemical shift prediction software, because few experimental data on this type of compounds are available. Furthermore, the potential n-type character of these derivatives is verified using electrochemical measurements. In addition, the low-bandgap character of conjugated polymers containing the thiazolothiazole unit is demonstrated by performing an electropolymerization. Copyright (C) 2010 John Wiley & Sons, Ltd.