KTiOPO₄ (KTP) is a classic commercial nonlinear optical (NLO) crystal, but its narrow bandgap (3.52 eV) prevents its practical application in the ultraviolet (UV) region. Many trials to widen the narrow bandgap of KTP have failed in the past few decades. A chemical cosubstitution strategy was implemented to design new members of the KTP-type family as potential UV NLO materials. First, a novel centrosymmetric KTP-type compound NH₄SbFPO₄·H₂O with a sharply enlarged bandgap (5.01 eV) was obtained through three-site aliovalent substitution. Second, the noncentrosymmetric NH₄SbF₂SO₄ was synthesized by the introduction of more F⁻ anions to destroy the crystal symmetry and SO₄²⁻ to replace PO₄³⁻ for balancing the charge in NH₄SbFPO₄·H₂O, which realized the transformation from a visible phosphate system to solar blind UV sulfate system for KTP-type family NLO materials. The preliminary experimental results indicated that NH₄SbF₂SO₄ is a promising solar blind UV NLO material. The first-principles calculations revealed that the sharply enlarged bandgap resulted from the substitution of the transition metal cations with the main group metal cations and the introduction of F⁻ anions with high electronegativity.