Abstract: | Two mixed‐metal gallium iodate fluorides, namely, α‐ and β‐Ba2[GaF4(IO3)2](IO3) ( 1 and 2 ), have been designed by the aliovalent substitutions of α‐ and β‐Ba2[VO2F2(IO3)2](IO3) ( 3 and 4 ) involving one cationic and two anionic sites. Both 1 and 2 display large second‐harmonic generation responses (≈6×KH2PO4 (KDP)), large energy band gaps (4.61 and 4.35 eV), wide transmittance ranges (≈0.27–12.5 μm), and high relevant laser‐induced damage thresholds (29.7× and 28.3×AgGaS2, respectively), which indicates that 1 and 2 are potential second‐order nonlinear optical materials in the ultraviolet to mid‐infrared. Our studies propose that three‐site aliovalent substitution is a facile route for the discovery of good NLO materials. |