The optical properties of electrochemically synthesized P3HT films were studied. After the synthesis, the samples were divided into two groups: as prepared (P3HT-E) and the chemically reduced (dedoped) in a basic medium (P3HT-D). These films were characterized by photoluminescence (PL), Raman and photoluminescence time decay techniques. Comparing the PL spectra of the films, it is noted that P3HT-D has a higher PL intensity. The films were exposed to a continuously incident 405 laser and the PL spectra were monitored every 10 min. For both samples, the photoluminescence intensity along the photo-irradiation showed an increase, although the P3HT-E sample presented a greater increase. Regarding the Raman spectra before and after the photo-irradiation, it was noticed that for P3HT-D there were no changes, whereas P3HT-E showed significant changes. The Raman spectrum of P3HT-E sample at the photo-irradiated point was very similar to the Raman spectrum of P3HT-D. Thus, it was proposed that laser irradiation induces a reduction process similar to chemical reduction. Although both processes lead to an increase in the PL intensity, there is a difference in the position of the emission bands. Unlike chemical doping, the photoreduction does not remove the charge transfer complexes of the polymer matrix, but only breaks their bond with the backbone chain. From the data of PL decay, it was observed that in the film P3HT-E, there was a predominance of longer times, evidencing the presence of barriers for the energy transfer, while, for the P3HT-D, the contribution of shorter decay times predominates, evidencing a greater energy transfer between the chains.