Silver bismuth iodide (Ag–Bi–I) light absorbers are interesting candidates as lead-free and low-toxic metal-halide materials for solar cell applications. In this work, the partial exchange of bismuth, Bi, with antimony, Sb, is investigated in samples prepared from a solution targeting stoichiometry AgBi₂I₇. Samples with a gradually increased exchange of Bi by Sb are prepared and light absorption measurements show that the absorption edge is gradually blue-shifted with increasing the amount of Sb. This trend in the shift in combination with the X-ray diffraction and X-ray photoelectron spectroscopy measurements, suggest that new materials with a mixture of Sb and Bi are formed. The density functional theory based electronic structure calculations reproduce the trend observed in the experiments when including spin–orbit coupling, which indicates the importance of relativistic effects in these materials. X-ray photoelectron spectroscopy is used to characterize the materials, and confirms the exchange of Bi to Sb in the samples. When Sb is included in the material, the grain size changes between 50 and 200 nm and the solar cell performance also changes. An optimal power conversion efficiency with excellent reproducibility and stability is obtained for a solar cell with the ratio of Sb/Bi equal to 3.