Studies on septithiophenes are relatively rare compared to the available detailed investigations of sexithiophenes. The balance is redressed here by a report of the synthesis, electrochemistry and spectroscopic properties of a new alpha,omega-disubstituted septithiophene and two pyrrole-containing septithiophene analogues. Two different routes are described by which it was attempted to impart solubility in organic solvents to septithiophenes-one unsuccessful and one successful. Evidence of an unusual three-electron transfer process is also presented.