Rational design and tailored synthesis of noncentrosymmetric compounds with nonlinear optical (NLO) properties, especially in the deep-ultraviolet (deep-UV) region, remains a great challenge. Herein, we report on the development of a modified fluoro-solvo-hydrothermal method with two additive reagents (trimethylamine and NaF solution) as the solvents, using BaFe(PO4)(OH) (P2(1)2(1)2(1),) as the prototype, for the rational design and tailored synthesis of the first deep-UV fluorinated orthophosphate, BaZn(PO4)F. It crystallizes in the polar space group Pna2(1) and exhibits transparency down to deep-UV region (<190 nm) with SHG effect at 0.26 x KH2(PO4). Its structure is built from strictly alternating ZnO4F trigonal bipyramids and PO4 tetrahedra, resulting in a four-connected ABW-type zeolite framework. First-principles calculations confirm the deep-UV absorption edge and reveal that ZnO4F plays an essential role in the NLO properties. The synergetic effect of Zn and F atoms leads to its more polar crystal structure, much deeper absorption edge, and better SHG effect than the prototype.