Abstract We have developed a new synthetic protocol for the unsymmetrically alkylated and halogenated terthiophenes 5 and 10. To demonstrate their usefulness as building blocks for well-defined oligothiophenes, we synthesized a series of seven new sexi-, septi-and octithiophenes. Terthiophene 5 could be dimerized to the didecylsexithiophene In6 and terthiophene 10 to sexithiophene Out6, respectively, by the use of nickel catalysis. ...