Introduction of the Cl(-) anion in the borate systems generates a new perovskite-like phase, K(3)B(6)O(10)Cl, which exhibits a large second harmonic response, about four times that of KH(2)PO(4) (KDP), and is transparent from the deep UV (180 nm) to middle-IR region. K(3)B(6)O(10)Cl crystallizes in the noncentrosymmetric and rhombohedral space group R3m. The structure consists of the A-site hexaborate [B(6)O(10)] groups and the BX(3) Cl-centered octahedral [ClK(6)] groups linked together through vertices to form the perovskite framework represented by ABX(3).