The wx-AMPS simulation software is used to model and simulate the Schottky perovskite thin film solar cells. The front and back electrodes with different work functions are applied to the Schottky perovskite solar cells to study the effect of band structure on the performance of solar cells. The results show that in a range from 3.8 to 4.4 eV, as the work function of the front electrode decreases, the conversion efficiency of the Schottky solar cells gradually increases. When the work function of the front electrode is low, the electric field strength is large, which facilitates the transport of carriers in the light-absorbing layer of the perovskite and reduces the carrier recombination rate of the perovskite layer. In addition, the recombination ratio of the light absorbing layer is reduced due to the increase of the electric field strength, and the parallel resistance is increased to a certain extent thereby increasing the FF and improving the output efficiency of the battery. At the same time, when the current electrode work function is maintained at 3.8 eV, in a range from 4.3 to 5.5 eV, the higher the work function of the back electrode, the greater the conversion efficiency of the Schottky solar cell is. This conduces to the band alignment in contact between perovskite and back electrode. Under the premise that the common electrode Au is used as a back electrode, the work function of the front electrode is 3.8 eV and the conversion efficiency of the Schottky perovskite solar cell is 17.93%. In addition, by using the optimized front and rear contact electrodes, the quality of the perovskite layer material, thus the performance of the solar cell can be further improved. Doping till a certain concentration and removing the defects of the perovskite layer, the conversion efficiency of the solar cell with a thickness of 500 nm can be increased from 17.93% to 20.1%. The simulation results show that the Schottky perovskite thin film solar cells can obtain excellent performance with simple device structure and have great potential applications.