Four new organically templated layered vanadyl(IV) phosphates, (Hcha)VOPO4 center dot 0.5H(2)O (cha = cyclohexylamine) (1), (Hchpa)VOPO4 center dot 0.5H(2)O (chpa = cycloheptylamine) (2), (Hcha)(0.5)(Hchpa)(0.5)VOPO4 center dot 0.5H(2)O (3), and (H(2)aepip)-[(VOPO4)(2)(H2O)] center dot H2O (aepip = N-(2-aminoethyl)piperazine) (4), have been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, magnetic susceptibility, and electron paramagnetic resonance (EPR) spectroscopy. They displayed a large interlayer gap propped up by an unprecedented double-tiered monoamine in vertical angles generating the lightest layered VPO material ever prepared and characterized. The anionic [VOPO4](-) sheets for all four compounds are constructed by a common secondary building unit consisting of one copper-acetate-type {((VO)-O-IV)(2)(mu(2)-PO4)(4)} cluster and two vanadium polyhedra. The d(1) state was confirmed by both magnetic susceptibility studies and EPR spectra. Moreover, compounds 1 and 4 showed antiferromagnetism with T-N at 30 K, the highest ever observed in layered vanadyl phosphates. The structural relationship, template arrangement, magnetic property, thermal stability, and correlation between interlayer gaps and densities are discussed. Compounds 1-3 crystallized in the monoclinic space group P2(1)/c (no. 14) with Z = 8, whereas compound 4 crystallized in the orthorhombic space group Pbca (no. 61) with Z = 4. Crystal data of 1, a = 16.3461(9) angstrom, b = 14.2641(8) angstrom, c = 9.4037(5) angstrom, beta = 94.519(1)degrees, V = 2185.80(2) angstrom(3); 2, a = 17.0773(5) angstrom, b = 14.3449(4) angstrom, c = 9.4251(3) angstrom, beta = 93.976(1)degrees, V = 2303.3(1) angstrom(3); 3, a = 16.6765(4) angstrom, b = 14.2927(3) angstrom, c = 9.4120(3) angstrom, beta = 95.389(1)degrees, V = 2233.5(1) angstrom(3); 4, a = 14.2517(9) angstrom, b = 9.4012(6) angstrom, c = 24.442(2) angstrom, V = 3274.8(4) angstrom(3).