The invention relates to a selenium antimony sulfide thin film solar cell with a 3D structure and a preparation method thereof, and belongs to the technical field of cell preparation. The thin film solar cell comprises substrate glass, a TiO2 layer, a BaTiO3 thin film layer, a Sb2 (S, Se) 3 thin film layer, a hole transport layer and an electrode layer which are sequentially stacked from bottom to top. The invention further discloses a preparation method of the Sb2 (S, Se) 3 thin film solar cell, the TiO2 layer of the prepared Sb2 (S, Se) 3 thin film solar cell is of a 3D-TiO2 array structure, pn junctions are formed by the TiO2 layer and the Sb2 (S, Se) 3 thin film layer, the BaTiO3 thin film serves as a passivation layer to be inserted between the pn junctions, and recombination of heterojunctions at an interface is reduced. The BaTiO3 thin film layer and the TiO2 layer form a double-buffer-layer structure, the width of a depletion layer is increased, and the open-circuit voltage of the cell can be effectively improved. And the ferroelectricity of BaTiO3 is utilized, so that the separation capacity of current carriers and the open-circuit voltage of the battery are improved. And the thickness of the BaTiO3 film is relatively small, so that the problem of high internal resistance of the battery caused by poor conductivity of BaTiO3 is solved based on the quantum tunneling effect.