The invention provides a TiO2/BaTiO3/RGO ternary composite photoelectric film and a rapid in-situ preparation method and application thereof, and belongs to the field of material synthesis. The high-performance TiO2/BaTiO3/RGO ternary composite photoelectric film is prepared according to a single step of obtaining a TiO2 ordered nanotube array substrate by anodic oxidation on a titanium foil, taking a hydrothermal method as a basis, employing microwave as an energy source, performing reaction of the TiO2 ordered nanotube array substrate in a precursor mixed solution of Ba(OH)2 and GO, performing in-situ reaction on a part of the TiO2 ordered nanotube array substrate to generate BaTiO3 by controlling a reaction parameter and simultaneously performing in-situ reduction on RO with high dispersibility. By the TiO2/BaTiO3/RGO ternary composite photoelectric film, the problems of unfavorable dispersibility of graphene, poor photoelectric property of TiO2, long hydrothermal synthesis time and the like are effectively solved, and the application of the TiO2 composite material in the field of photo-generated negative electrode protection is promoted.