Exploring novel functional materials via chemical substitution-oriented design is an emerging strategy. The method can be expanded to the discovery of high performance ultraviolet (UV) nonlinear optical (NLO) solid state materials by a careful tuning of the substituted atoms. This minireview presents a brief introduction to chemical substitution-oriented design including single-site substitution, dual-site substitution, and multisite substitution. Several state-of-the-art UV NLO materials such as K₃VO(O₂)₂CO₃-type, KBe₂BO₃F₂ (KBBF)-type, Ca₅(PO₄)₃(OH)-type, and KTiOPO₄ (KTP)-type phases successfully discovered by the chemical substitution method are discussed.

Ba ₂ NO ₃ (OH) ₃ exhibits a perfect balance of a large SHG coefficient, a short UV absorption cutoff edge, an appropriate birefringence, and stable physicochemical properties.

A noncentrosymmetric nitrate Sr ₂ (OH) ₃ NO ₃ has been synthesized which is the first nitrate as a promising deep-UV nonlinear optical material.