The photophysics and nonlinear absorption behaviour of a series of α, ω-dithienyl polyenes were studied in chloroform and n-octane solutions. Steady state fluorescence, fluorescence lifetime and quantum yield measurements were made. The fluorescence quantum yields were significantly lower than those of the corresponding ax,o-diphenyl polyenes. Among the dithienyl polyenes, 3,3′-substituted polyenes exhibited stronger fluorescence than those of the 2,2′-substituted. Nonlinear optical absorption experiments showed evidence of two photon absorption.