In order to generate deep-ultraviolet (DUV, lambda < 200 nm) coherent light, many DUV-transparent nonlinear optical (NLO) compounds have been synthesized experimentally over the past few decades, most of which contain alkali or/and alkaline earth metal cations. However, to date, practical DUV NLO materials beyond KBe2BO3F2 (KBBF) are still very scarce. In this work, based on analysis of the DUV NLO effect induced by the A-site alkali and alkaline earth metal cations, we attempt to expand the options for DUV NLO compounds from a molecular engineering point of view. Accordingly, a useful strategy is proposed to design densely stacked layered structures without A-site cations as new and promising DUV NLO materials. Along with the available experimental and first-principles calculation results, it is demonstrated that layered structures in which the A-site cations are removed, such as Be2BO3F, Be2CO3F2, AlCO3F, SiCO3F2, AINO(3)F(2), PBO3F2, and PB3O6F2, whether real or hypothetical, exhibit excellent DUV NLO performances. Based on the findings, our strategy may open up new opportunities for the design and exploration of high-performance DUV NLO materials beyond KBBF.