In summary, theoretical calculations and experimental analysis show that both π-conjugated organic cation with local polarity and tetravalent rare-earth cerium cations without lone pair electrons could be considered as good FBU for achieving a balance between SHG response and LIDT of metal halides, providing some unprecedented opportunities for designing novel NLO crystals. Additionally, integrating of a high coordination number of Zr⁴⁺ cation and a higher proportion of F atom would facilitate the acquisition of shorter UV cutoff edges. Therefore, we believe that if we can control the order arrangement and density of these microscopic groups in the crystal structure, the vigorous development of laser technology and its related fields will be undoubtedly promoted.