Melt growth of BaSi2 by the vertical Bridgman (VB) growth method was initiated from barium metal (3 N grade) and semiconductor-grade silicon. Because Ba is highly reactive at the growth temperature (≈1500 K), the crucible materials were chosen to avoid chemical reactions and sticking between the crucibles and the molten and vapor Ba. Crucibles made of molybdenum, quartz, alumina, SiNx-coated quartz, chemical vapor deposition (CVD) pyrolytic graphite (PG), and chemical vapor deposition SiC-coated graphite were examined, and the semiconductor orthorhombic BaSi2 was obtained in quartz, alumina, and molybdenum crucibles. The crystalline forms of the grown crystals depend on the crucible materials and growth conditions.