Under solvothermal/surfactant-thermal conditions, two new open-framework borogermanate and galloborate, centrosymmetric (Hdima)(2)[Ge5B3O15(OH)] (1; dima = dimethylamine) and noncentrosymmetric Na4Ga3B4O12(OH) (2), were obtained and characterized. Compound 1 contains an unusual basket-shaped Ge5B3O18(OH) cluster and displays a 3D open -framework layered structure. Compound 2 shows an interrupted 3,4-connected network constructed by alternately linked BO3 units and Ga3+ ions and displays weak second-harmonic generation response.