Mixed-halide organolead perovskites (MAPbX3) are of great interest for both single-junction and tandem solar cells because of their wide band gap. In this study, we investigate the family of mixed iodide/bromide (I/Br) and bromide/chloride (Br/Cl) perovskites, revealing the strong influence of halide substitution on electronic properties, morphology, film composition, and phase segregation. A qualitative blue shift with the I → Br → Cl series was observed, with the resulting optical absorption ranging from 420 to 800 nm covering nearly the entire visible region. The ionization potential increases from ≈6.0 to ≈7.0 eV as the halide composition changes from I to Br. However, with Cl components, the valence band position shows little variation, while the conduction band minimum shifts to a lower value with increasing Cl concentration. By collecting XPS spectra as a function of the sputtering depth, we observed halide segregation in both I/Br and Br/Cl mixed-halide perovskite films, where the large halide ion (I in the I/Br mix or Br in the Br/Cl mix) is preferentially found on the surface of the film and the smaller halide ion (Br in the I/Br mix or Cl in the Br/Cl mix) accumulates at the bottom of the film. These differences in the band structure, electronic properties, morphology, and film composition impacted the device performance: a decreased short-circuit current density and increased open-circuit voltage were observed with the I → Br → Cl series. This study highlights the role of halides in the band structure and phase segregation in mixed-halide perovskite solar cells and provides a foundational framework for future optoelectronic applications of these materials.