One of the challenges in fabricating organic semiconductor thin film is to produce bettermolecular ordering that compromise its electronic properties. Molecular ordering of amorphous thin film can be improved in many ways. Here, high molecular weight polylactic acid (PLA) is introduced as binding matrix to promote 3'''-didodecyl-2,2':5',2'':5'',2'''-quaterthiophene (4T) film’s homogeinity across indium tin oxide (ITO) surface. Molecular ordering of the spin coated biodegradable PLA and 4T blend film processed at ambient atmosphere was studied using two vibrational spectroscopy methods. The complementary analysis of infrared absorption spectrum and Raman spectrum had identified several vibrational modes contributed by thiophene rings and alkyl functional groups. The Raman analysis implied there is a slight change of thiophene ringsʼ molecular orientation due to compressive stress after introduction of polymer. Microscopic characteristics of oligothiophenes especially at the π-π conjugated backbones contained crucial information in order to exploit the oligothiophene as flexible electronics devices.