The construction of nonlinear optical materials featuring asymmetric transmission of light is of great technological importance for various applications, including optical switching and optical power limiting. A significant challenge is the scalable fabrication of material candidates with good photochemical stability, high optical transmittance, and excellent optical limiting performance. Here, we present a nanocrystallization avenue for constructing hybrid optical limiting materials that exhibit ultrafast and robust optical limiting performance. The experimental results show that the controllable relaxation of a niobate glass may lead to the clustering of Nb-O units and contracting of the bandgap. It results in the notable improvement in nonlinear optical properties, including the enhanced saturation irradiance (380GW/cm(2)), doubly increased nonlinear coefficient, and decreased limiting threshold (200GW/cm(2)). Our results suggest a promising material that exhibits promising applications for protecting eyes and sensitive components from laser-induced damage.