The first chiral zeolite-like galloborate, K-2[Ga(B5O10)]center dot 4H(2)O, has been synthesized by a mild solvothermal method and characterized by Fourier transform IR, energy-dispersive spectroscopy, thermogravimetric/differential thermal analysis, and single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic system with space group C222(1). The structure possesses a 3D open framework constructed by B5O10 clusters and GaO4 units and contains large odd 11-ring channels.