A series of a novel beryllium-free KBBF family of nonlinear-optical materials AZn(2)BO(3)X(2) (A = K, Rb and X = Cl; A = Na, K, Rb and X = Br) were successfully synthesized through molecular engineering design, and single crystals of AZn(2)BO(3)Cl(2) (A = K, Rb) were grown by a spontaneous nucleation technique from self-flux systems. As a representative for the halogen KBBF family of crystals, KZn2BO3Cl2 features the infinite lattice layer [Zn2BO3Cl2](infinity) made up of BO3 and ZnO3Cl anionic groups, and the in-layer BO3 groups are completely coplanar and well-aligned. Besides, KZn2BO3Cl2 exhibits high transmittance in the range of 300-2000 nm with a UV-transmission cutoff of around 200 nm according to transmission spectra. The compounds of AZn(2)BO(3)Cl(2) (A = K, Rb) are both phase-matchable with powder second harmonic-generation efficiencies of 1.3 and 1.17 times that of KH2PO4 for KZn2BO3Cl2 and RbZn2BO3Cl2, respectively, which are similar to that of KBBF.