AbstractRealization of highly tunable second-order nonlinear optical responses, e.g., second-harmonic generation and bulk photovoltaic effect, is critical for developing modern optical and optoelectronic devices. Recently, the van der Waals niobium oxide dihalides are discovered to exhibit unusually large second-harmonic generation. However, the physical origin and possible tunability of nonlinear optical responses in these materials remain to be unclear. In this article, we reveal that the large second-harmonic generation in NbOX₂ (X = Cl, Br, and I) may be partially contributed by the large band nesting effect in different Brillouin zone. Interestingly, the NbOCl₂ can exhibit dramatically different strain-dependent bulk photovoltaic effect under different polarized light, originating from the light-polarization-dependent orbital transitions. Importantly, we achieve a reversible ferroelectric-to-antiferroelectric phase transition in NbOCl₂ and a reversible ferroelectric-to-paraelectric phase transition in NbOI₂ under a certain region of external pressure, accompanied by the greatly tunable nonlinear optical responses but with different microscopic mechanisms. Our study establishes the interesting external-field tunability of NbOX₂ for nonlinear optical device applications.