Single crystals of a new ternary lithium chalcogenide LiGaSe2were grown by an improved directional solidification technique. The typical as‐grown crystal has dimensions of about 4 mm cubed and shows a transparent light yellow color. We infer that LiGaSe2crystallizes in the &bgr;‐NaFeO2structure having an orthorhombic unit cell (a= 6.833 A˚,b= 8.227 A˚, andc= 6.541 A˚) by powder x‐ray diffraction. The melting point was determined by differential thermal analysis to be 846 °C. The energy band gap of LiGaSe2at room temperature was determined by optical reflectance measurements to be 3.65 eV.