Four new 2D layered quinary sulfides, Ba₄F₄CrGa₂S₆ (1), Ba₄F₄MnGa₂S₆ (2), Ba₄F₄FeGa₂S₆ (3) and Ba₄F₄MnIn₂S₆ (4), have been synthesized by the traditional solid state reaction method. Single crystal X-ray diffraction analyses show that the isostructural complexes 1, 3 and 4 belong to the Ba₂F₂Fe_1.5S₃ structure type and crystallize in the space group Pnma of the orthorhombic system, whereas the complex 2 crystallizes in the space group Cmca. The crystal structures of the four compounds can be viewed as the alternated stacking of the fluorite type [Ba₂F₂]²⁺ blocks and the newly discovered [X_0.5GaS₃]²⁻ or [X_0.5InS₃]²⁻ blocks. First-principles electronic structure calculations performed with DFT indicate that the title compounds are semiconductors with the band gaps of 1.83, 3.21, 1.16 and 2.93 eV for 1, 2, 3 and 4, respectively.