Two novel aluminophosphates, Al2(HPO3)2.26(HPO4)0.74 and Al2(PO4)2(H2O)4, were synthesized using hydrothermal methods, while another polar aluminophosphite, Al[P2O3(OH)3](H2O), was obtained via a low-temperature flux method. They crystallized in the nonpolar space group P63/m and polar space groups of P212121 and P63mc, respectively. The basic units of Al2(HPO3)2.26(HPO4)0.74 consist of PO4/PO3 and AlO6 groups, in which one AlO6 octahedron coordinated with six PO4 tetrahedra/PO3 pyramids and one PO4 tetrahedron/PO3 pyramid linked three Al2O9 dimers. However, the fundamental units for Al2(PO4)2(H2O)4 are PO4 tetrahedra, AlO6 octahedra, and AlO5 trigonal bipyramids, in which one PO4 tetrahedron is connected with three Al2O10 dimers and one Al2O10 dimer is linked with six PO4 tetrahedra, forming its novel three-dimensional framework structure. Importantly, Al[P2O3(OH)3](H2O) and Al2(PO4)2(H2O)4 demonstrate moderate second-harmonic generation effects in the UV region, with ∼0.15 and ∼0.68 × KDP, respectively. The syntheses and topological structures, compositional analysis, thermal behavior, FT-IR spectral characterization, Raman spectral analysis, and UV-vis diffuse reflectance along with the NLO performances of Al2(PO4)2(H2O)4 and Al[P2O3(OH)3](H2O) are discussed.