Hybrid organic–inorganic solar absorbers are currently the subject of intense interest; however, the highest-performing materials contain Pb. Here we assess the potential of three Sb-based semiconductors: (i) Sb2S3, (ii) Cs2Sb8S13, and (iii) (CH3NH3)2Sb8S13. While the crystal structure of Sb2S3 is composed of 1D chains, 2D layers are formed in the ternary cesium and hybrid methylammonium antimony sulfide compounds. In each case, a stereochemically active Sb 5s2 lone pair is found, resulting in a distorted coordination environment for the Sb cations. The bandgap of the binary sulfide is found to increase, while the ionization potential also changes, upon transition to the more complex compounds. Based on the predicted electronic structure, device configurations are suggested to be suitable for photovoltaic applications.