The solvothermal synthetic exploration of the Bi-S-halogen phase space resulted in the synthesis of two bismuth sulfohalides with common structural motifs. Bi13S18I2 was confirmed to have the previously reported composition and crystal structure. In contrast, the bromide analogue was shown to have a formula of neither Bi19S27Br3 nor Bi13S18Br2, in contrast to the previous reports. The composition, refined from single crystal X-ray diffraction and confirmed by elemental analysis, high-resolution powder X-ray diffraction, and total scattering, is close to Bi13S17Br3 due to the partial S/Br substitution in the framework. Bi13S18I2 and Bi13S17Br3 are n-type semiconductors with similar optical bandgaps of ∼0.9 eV but different charge and heat transport properties. Due to the framework S/Br disorder, Bi13S17Br3 exhibits lower thermal and electrical conductivities than the iodine-containing analogue. The high Seebeck coefficients and ultralow thermal conductivities indicate that the reported bismuth sulfohalides are promising platforms to develop novel thermoelectric materials.