A new acentric borate, K2 Na3 [{B6 O10 (OH)}-{B3 O4 (OH)3 }] ⋅ H2 O (1) has been made under solvothermal condition. 1 has layered structure made by B6 O13 (OH)-based chains and B3 O5 (OH)3 -bridging clusters. Second-harmonic generation (SHG) measurements reveal that 1 is a phase-matchable nonlinear optical (NLO) material, showing the SHG signal intensity of 1.8 times that of KDP (KH2 PO4 ). Besides, UV-Vis diffuse reflectance spectrum shows that 1 has the short deep UV (DUV) absorption cutoff edge of 198 nm. Thermogravimetric analysis reveals it has good thermal stability. Also 1 represents firstly mixed oxoboron clusters-made 2D layered borate with NLO property.