The surface composition and morphology of FA0.85MA0.15Pb(I0.85Br0.15)3 films fabricated by the spin-coating method with different concentrations of NH2-POSS were investigated with atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), angle-resolved X-ray photoelectron spectroscopy (AR-XPS), and Fourier transform infrared spectroscopy (FTIR). It was found that the surface composition of the FA0.85MA0.15Pb(I0.85Br0.15)3 films was changed regularly through the interaction between NH2-POSS and the perovskite film. The corresponding surface morphological changes were also observed. When the concentration of NH2-POSS exceeded 10 mg/mL, a lot of cracks on the surface of the perovskite film were observed and the surface morphology was damaged. The surface composition and its distribution can be adjusted by changing the concentration of NH2-POSS and the proper concentration of NH2-POSS can substantially improve the quality of perovskite film.