Two new aluminoborates, NaKCs[AlB7O13(OH)]·H2O (1) and K4Na5[AlB7O13(OH)]3·5H2O (2), have been hydro(solvo)thermally made with mixed alkali metal cationic templates. Both1and2crystallize in the monoclinic space groupP21/nand contain similar units of [B7O13(OH)]6−cluster and AlO4tetrahedra. The [B7O13(OH)]6−cluster is composed of three classical B3O3rings by vertex sharing, of which two of them connect with AlO4tetrahedra to constitute monolayers, and one provides an O atom as a bridging unit to link two oppositely orientated monolayers by Al-O bonds to form 3D porous-layered frameworks with 8-MR channels. UV-Vis diffuse reflectance spectra indicate that both1and2exhibit short deep-UV cutoff edges below 190 nm, revealing that they have potential applications in deep-UV regions.