The first Ba-containing hydrated vanadate as nonlinear optical (NLO) material, BaV2O6·H2O, was synthesized by facile hydrothermal method. The single-crystal X-ray diffraction result shows that this compound crystallizes in the acentric orthorhombic space group of P212121 with cell parameters a = 7.3993(6) Å, b = 8.9934(7) Å, and c = 9.7206(8) Å. UV–vis-IR diffuse reflectance spectrum shows that the compound has a large bandgap of 4.60 eV and moderate transparency range. The title compound shows second-harmonic generation (SHG) efficiency about 0.5 times of KH2PO4 (KDP). The structure-property relationship of BaV2O6·H2O was clarified by the first-principles studies.