Two three-dimensional (3D) zeolitic open-framework aluminoborates (ABOs) [Zn(ma)(en)(2)][AlB5O10] (1) and [Zn(ma)(en)(2)][AlB6O11(OH)] (2) (ma = methylamine, en = ethylenediamine) were successfully made under solvothermal conditions, which represent the first examples using similar metal complex (MC) with mixed amines as the structure-directing agents in ABOs. Notice that the central atom in the MC is coordinated by mixed amines is uncommon. However, they exhibit distinctly different structures: 1 crystallizes in a centrosymmetric [Al(B5O10)](n)(2n-) zeolitic framework built by pentaborate (B5O10) clusters and AlO4 tetrahedra, exhibiting a 4-connected cag topology, while 2 contains hexaborate (B6O11(OH)) clusters and AlO4 groups, further alternately joined to form a noncentrosymmetric [AlB6O11(OH)](n)(2n-) zeolitic framework with 7-/9-, 8-/10-ring helical channels and large 13-ring channels, showing a dia topology. Nonlinear optical (NLO) determination showed that 2 exhibits good second-harmonic generation response of similar to 19 x KH2PO4 and is phase-matchable, combining the short UV cutoff edge, making 2 a potential UV NLO material.