A new inorganic-organic hybrid solid, [Zn(dap) 2 ]-[AlB 5 O 10 ], combining the structural features of 3D openframework inorganic solids and 2D metal-organic coordination polymers has been synthesized under solvothermal conditions. The compound displays extensive luminescence and moderate second-harmonic-generation efficiency.Crystalline open-framework inorganic solids are of current interest for their potential application in catalysis, separation, and ion exchange. [1] Aluminosilicate molecular sieves are the most well-known such materials with four-connected networks. Recently, great effort has been devoted to the synthesis of new zeotype materials by replacing SiO 4 tetrahedra with tetrahedral oxoboron clusters. [2] A number of openframework aluminoborates have been prepared in the presence of amines, inorganic cations, and discrete metal complexes as the structure-directing agents. [3] Unlike fourconnected aluminosilicates, open-framework aluminoborates often contain unique BO 3 triangles in their structures. Such planar building units are highly desired in the design and synthesis of new optical materials with second-harmonicgeneration (SHG) response. [4] A notable example is b-BaB 2 O 4 (BBO), which exhibits excellent second-order nonlinear optical (NLO) properties. [5] It is expected that openframework aluminoborates may integrate zeolitic porosity with the extraordinary optical properties of borate materials.Functional coordination polymers constructed from metal ions and organic ligands are another expanding area for the exploration of porous materials. [6] The designable nature of organic ligands and their rich coordination geometries indicate that a huge number of porous coordination networks