A method of forming a Pb-free perovskite film is provided, the method based on vacuum evaporation and comprising: first depositing a first material comprising Sn halide on a substrate to form a first layer; second depositing a second material comprising organic halide to form a second layer on the first layer to obtain a sequentially-deposited two-layer film on the substrate; and annealing the sequentially-deposited two-layer film on the substrate. During the annealing, the first and second materials inter-diffuse and react to form the Pb-free perovskite film. The second layer is formed to cover the first layer so as to prevent the first layer from air exposure. The solar cell device including the Pb-free perovskite film formed by using the present method exhibits good stability.