The optical properties and electronic structures of an organic semiconductor sexithiophene have been investigated with ultraviolet-visible spectroscopy, cw photospectroscopy and time-resolved photospectroscopy, respectively. Sexithiophene in dilute tetrahydrofuran solutions can absorb photons at 400 nm while it can give off strong green photoluminescence at 550 nm under the excitation of 325 nm ultraviolet light. With the assistance of calculated electronic structures and pump-and-probe characterization, our results indicate that both the optical absorption and the light emission of the sexithiophene are controlled by the p-conjugation of the oligothiophene.