Six isostructural antiperovskite-derived chalcohalides, Ba(2)MQ(3)X (M = As, Sb; Q = S, Se; X = Cl, Br, I), crystallizing in the space group Pnma, have been synthesized by solid-state reactions. The crystal structure features a 3D framework with the [XBa5](9+) disordered square pyramids as building blocks and [MQ(3)](3-) units filling the interspace. [XBa5](9+) disordered square pyramids are edge-sharing along [OM], derived from, the fusing of the two pyramids in octahedral [XBa6](11+). Surprisingly, Ba2AsS3X (X = Cl, Br, I) show almost the same optical band gap of 2.80 eV, and Ba2AsSe3X (X = Br, I) also have a similar band gap of 2.28 eV. The optical band gap of Ba2SbS3I is 2.64 eV. First-principles calculations reveal that the optical absorption is attributed to the transitions between Q np at the valence band maximum (VBM) and M np-Q np at the zonthiction band minimum (CBM). These compounds also possess interesting photoluminescence properties with splitting emission peaks on excitation at 200 nm.