Inorganic metal chalcohalides, as significant semiconductor materials, have emerged as promising candidates for photoelectric applications. Herein, a new type of quaternary chalcohalide, [Ba4X][In19S32] (X = Cl, Br), has been discovered using the high-temperature halide salt flux method. Single-crystal X-ray diffraction analysis reveals that they are isostructural and crystallize in the tetragonal space group I41/amd (no. 141) featuring the octahedral hole formed by six [InS4]5- tetrahedra filled with a [ClBa4]7+ polycation, surrounded by a three-dimensional covalent framework formed by interconnecting [InS6]9- octahedra through corner-sharing and edge-sharing. Moreover, [Ba4Cl][In19S32] and [Ba4Br][In19S32] exhibit wide optical bandgaps of 2.70 eV and 2.46 eV, respectively, and moderate birefringences (0.044 @ 2100 nm and 0.042 @ 2100 nm, respectively). Specifically, [Ba4X][In19S32] (X = Cl, Br) display remarkable photocurrent responses under simulated solar-light illumination, implying their potential for photocatalytic applications. Theoretical calculations were employed to understand the interrelationship between the optical properties and electronic structure. The study on the synthesis and structure-property relationship analysis of inorganic metal chalcohalides provides new insight into the exploration of promising photoelectric materials.