Exploring new nonlinear optical materials with excess electron character is extremely important for promoting the application of excess electron compounds in nonlinear optics. Herein, by using density functional theory (DFT) computations, new superalkali-based alkalides Li₃O@[12-crown-4]M⁻ are designed as excess electron compounds. QTAIM studies suggest that the complexant interacts with alkali and superalkali clusters through non-covalent interactions. These complexes are thermodynamically stable and their interaction energies range from −33.40 ∼ −44.23 kcal mol^-1. The alkalide nature of these compounds is guaranteed by their HOMOs values and NBO charge analysis. Being excess electron compounds, these alkalides shows potential electronic properties. Their HOMO-LUMO gaps ranging from 0.17–0.27 eV. With excellent properties, these complexes show remarkable total hyperpolarizability (β_o) response (9.30×10⁴–5.26×10⁶au). Interestingly, the hyperpolarizability response is dependent on the size of alkali metals. The β_vec values are quite comparable to total hyperpolarizability at the same level of theory. Furthermore, the hyperpolarizability calculated through two-level model (β_tl) values show a trend similar to hyperpolarizability. Additionally, the dynamic hyperpolarizability response for EOPE effects is much pronounced at the dispersion frequency of 532 nm. The second hyperpolarizability response for the dc-Kerr constant is increased up to 2.75 × 10¹² au which is much higher than those of previously reported alkalides. Strikingly, the frequency-dependent NLO response shows dependence on alkalide character rather than the size of alkali metal (M). Moreover, the β_HRS value is recorded up to 2.16 × 10⁶ au. The significant dipolar contribution to hyperpolarizabilities Φβ(J = 1) are observed for these complexes.