The invention discloses an organic small-molecule donor photovoltaic material containing fluorinated benzotriazole as well as a preparation method and application of the organic small-molecule donor photovoltaic material. The organic small-molecule donor photovoltaic material has a structural formula as shown in formula I, wherein X is H or F; Z is O, S or Se; R1, R2 and R3 are independently selected from H, C1-C30 alkyl groups, C3-C30 naphthenic bases, C1-C30 alkoxy groups, C1-C30 alkyl sulphanyls, halogeneated C1-C30 alkyl groups, halogeneated C3-C30 naphthenic bases and halogeneated C1-C30 alkoxy groups; each of A1 and A2 is an organic conjugated unit; and n is a natural number from 1 to 10. The application of an organic photoelectric compound to the following functional energy devices including a solar battery, a field effect transistor, an organic light emitting diode and a photovoltaic device also belongs to the protection scope of the invention. The organic photoelectric compound provided by the invention is simple in synthesis step, easy to purify and determined in structure; and the organic photovoltaic device prepared from the organic photoelectric material provided by the invention has excellent photovoltaic property, and the photoelectric conversion efficiency can reach 9.5%.