Syntheses of new oligothiophenes which have cyano and hexyl groups at the ends of quarter- and ter-thiophenes are described. The observations of DSC and polarizing rnicroscopy indicate the presence of liquid-crystalline (LC) phases over a wide temperature range. The energy gaps are discussed on the basis of the absorption and photoluminescence (PL) spectra and cyclic voltammetry. Thin films of oligothiophenes fabricated by vacuum deposition are investigated by AFM and XRD measurements.