Three transitional-metal-substituted aluminophosphate molecular sieves, |(C3N2H5)8|[M8Al16P24O96] (denoted MAPO-LAU, M = Co, Mn, Zn), have been synthesized under solvothermal conditions in the presence of imidazole as the structure-directing agent. Their structures are determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction, inductively coupled plasma, thermogravimetric, and diffuse reflectance spectroscopy (UV-vis) analyses. The structure of MAPO-LAU is based on the strict alternation of MO4/AlO4 tetrahedra and PO4 tetrahedra through vertex oxygen atoms. Their frameworks are analogous to the zeotype LAU structure in which 33% of the aluminum sites are replaced by transitional-metal ions. The protonated imidazole cations resided in the 10-ring channels. These compounds show photoluminescent properties due to the existence of imidazole molecules in the structures. Magnetic measurements reveal that there is very weak antiferromagnetic interaction among the metal centers of MnAPO-LAU.