A Weyl semimetal is a novel crystal with low-energy electronic excitations that behave as Weyl fermions. It has received worldwide interest and was believed to have introduced the next era of condensed matter physics after graphene and three-dimensional topological insulators. However, it is not easy to obtain a single large-sized crystal because there are many nucleations in the preparation process. A bottom-seed CVT growth method is proposed in this paper, and we acquired the large-sized, high-quality NbAs single crystals up to 4 × 3 × 3 mm3 finally. X-ray diffraction and STEM confirmed that they are tetragonal NbAs, which the key is to using the seed crystal in a vertical growth furnace. Notably, the photoelectric properties of the crystal are obtained under the existing conditions, which paves the way for follow-up work.