Two new nonmetal borates, [(C2H10N2)]2[B14O20(OH)6] 1 and [C8H22N4][B5O6(OH)4]2 2, have been synthesized under mild conditions and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis and thermogravimetric analysis. Crystal data for compound 1: triclinic, space group P1, a = 8.4979(17), b = 8.8498(18), c = 10.065(2) , α = 95.01(3), β = 96.99(3), γ = 116.82(3)o, V = 661.8(3)3, Z = 1, Mr = 697.63, Dc = 1.751 g/cm3, μ = 0.163 mm-1, F(000) = 356, the final R = 0.0372 and wR = 0.0968 (I > 2σ(I)); and those for compound 2: monoclinic, space group P21/c, a = 9.1867(18), b = 14.118(3), c = 10.334(2) , β = 91.48(3)o, V = 1339.8(5) 3, Z = 2, Mr = 610.46, Dc = 1.513 g/cm3, μ = 0.135 mm-1, F(000) = 632, the final R = 0.0350 and wR = 0.0912 (I > 2σ(I)). For both 1 and 2, the anionic units are interlinked via O–H···O hydrogen bonds to form a 3D supramolecular network, while the protonated cations are located in the free space of the inorganic borate framework and interact with the anions by electrostatic attraction and extensive N–H···O hydrogen bonds.