When CsCl, BaS, BaO, V, and S are reacted in a solid-state reaction under inert conditions, pure powders and single crystals of senary CsBa6V4S12ClO4 can be obtained. Its unique crystal structure has the symmetry R (3) over barH (no. 148) and unit cell parameters a = 9.0575(2) and c = 28.339(1) angstrom. The crystal structure contains polar units [VS3O](3-) and a complex BaS7ClO2 coordination. The compound gets its deep-red color from a low-energy charge transfer, which can be explained by an electron transfer from S2- to V5+. In the near-infrared range, down-converted fluorescence occurs at 1.06 and 0.90 eV, and both emissions appear <450 ps after excitation at about 1.27 eV.