Four metal phosphites/phosphates crystal materials C8N4H34Al2P4O18 (1), C3N2H17GaP2O8 (2), H5In2P3O10 (3), and H9In2P3O13 (4) have been solvothermally synthesized by organic amines in the presence of mixed solvents. Structural analyses indicate that compound 1 and 2 show one-dimensional (1D) chain structures; compound 3 and 4 are three-dimensional (3D) inorganic open-framework indium phosphites. Organic amines show different mechanisms in the four compounds. The 2,2'-bipyridine organic amine acts as a template source and it breaks down small molecules, which enter into the structure of compound 1. For compound 2, 1,2-propanediamine has a role as protonated template and it forms a hydrogen bond with the inorganic skeleton structure. As for compound 3 and 4 without the organic template, the benzylamine and 2,2'-bipyridine mainly serve as structure-directing agent. Especially, compound 3 has an odd seven-ring channel, and compound 4 contains 3D intersecting six-ring, eight-ring, and 10-ring channels. X-ray diffraction (XRD), scanning electron microscopy (SEM), CHN, inductive coupled plasma (ICP), Infrared (IR), and thermal gravimetric (TG) analyze the four compounds.