An organic photoelectric semiconductor device including organic group VA salts in an organic salt-containing layer and a method for manufacturing the same are provided. The organic photoelectric semiconductor device includes: a first electrode; an organic active layer disposed over the first electrode; an organic salt-containing layer disposed over the organic active layer, where the organic salt-containing layer includes quaternary group VA salts of cations represented by the following formula (I) or derivatives thereof and anions; and a second electrode, disposed over the organic salt-containing layer, where, X, R1, R2, R3 and R4 are defined the same as the specification. Accordingly, the present invention can enhance the transmission of electrons and thus enhances the performance of devices.