Perovskite-based materials have been considered as the most promising materials in several solar-driven processes, especially photovoltaics. Some features such as high sunlight harvesting and improved carrier transport have been highlighted to have an impact on the efficiency of the above topics, but limited studies have pointed out their surface composition, which mainly influence the above abilities. As a starting point to recognize the surface environment and chemical states of these materials, x-ray photoelectron spectroscopy measurements were performed. Trication-mixed halide perovskite films based on Cs0.08MA0.18FA0.78PbBr0.42I2.58 were prepared by a one step process and deposited on an indium tin oxide substrate by spin-coating. Survey spectra, Pb 4f, I 3d, Br 3d, Cs 3d, C 1s, N 1s, Pb 4d, and Pb 5d core levels, and valence band spectra were measured for the semiconductor sample. Results exhibit symmetrical peaks, indicating that a homogenous solid solution was achieved. Main chemical states of this kind of perovskites such as Cs-Br and Pb-I species are also shown. We deduced that the later signals are associated with the [PbI6]4− octahedra existing in the perovskite lattice, while the former one is related to Cs+ bounded to [PbBr6]4− units on the perovskite surface. Interestingly, the NR4+ signal was also identified, associated with the presence of methylammonium and formamidinium cations.