A quaternary narrow-band-gap semiconductor, Ba2Cr4GeSe10, has been discovered by solid-state reaction. It features a new structure type and crystallizes in the triclinic space grout P (1) over bar (No. 2). The featured 2D anionic layers are constructed by condensed CrSe6 octahedra that are stacking along the c axis, with dispersed GeSe4 tetrahedra and located Ba2+ cations forming these layers. The energy-band structure shows a clear separation between the region of electronic conduction and the zone of electronic insulation. Significantly, an undoped Ba2Cr4GeSe10 sample shows a desirable low thermal conductivity K-T (0.51-0.87 W/m.K) and a high Seebeck coefficient S (351-404 mu V/K) and reaches a ZT approximate to 0.08 at 773 K.