The invention discloses a [2.1.3]benzoxadiazole photovoltaic material, and a preparation method and application thereof, and belongs to the technical field of photovoltaic materials. The structure is as shown in a formula (I). The invention also provides a preparation method and the application of the [2.1.3]benzoxadiazole photovoltaic material. During preparation of the photovoltaic material, a [2.1.3]benzoxadiazole (BO) organic electron donor unit with a terminal group being trifluoromethyl-phenyl is synthesized mainly by a stille coupling method, and the optical property and the electrochemical property of organic molecules are regulated and controlled by changing different side chain units. The synthesis route is simple, the cost is low, and the synthesis method has universality and can be popularized and applied to synthesis of other [2.1.3]benzoxadiazole materials; the [2.1.3]benzoxadiazole photovoltaic material has a larger conjugated structure, and wider ultra-violet visible absorbing spectrum and current carrier migration rate are expected to obtain; the [2.1.3]benzoxadiazole photovoltaic material has lower HOMO energy level, has high stability on oxygen and is favorable for preparation of solar battery devices with more stable performance.