A simple yet effective method based on methanol treatment is proposed to enhance the external quantum efficiency (EQE) of the photomultiplication type organic photodetector with a structure of Glass/ITO/PEDOT:PSS/P3H:PC71BM (100:1, wt./wt.)/Al. By modifying the PEDOT:PSS film surface with methanol, the EQE of photodetector significantly improved within a broad wavelength range of 300–700 nm. The maximum EQE of 25300% occurs at the wavelength of 350 nm in the methanol-treated device under −9 V bias, which more than doubles that (11500%) of the device without treatment. In addition, as a result of the methanol treatment, the detectivity of the device improved from 3.72 × 1012 to 7.24 × 1012 Jones at −9 V under 350 nm light illumination. The large improvement is attributed to the fact that the methanol treatment can improve the electrical performance of the PEDOT:PSS by removing the insulator PSS within the film and also result in PC71BM aggregations in the active layer. The latter can enhance the tunneling hole injection by the intensified energy-level bending, which is induced by both the trapped electrons in these aggregations and accumulated ones near Al electrode. As a result, the modification of both the PEDOT:PSS layer and the active layer increases the response current, resulting in the EQE improvement.