Designing superatoms with special structural and photoelectric properties is vital for the applications in multiple fields including condensed matter physics, nanomaterials science etc. In this study, the effects of an oriented external electric field (OEEF) on the geometry, electronic properties, photoelectron spectrum (PES), and nonlinear optical (NLO) response of the main group metal‐doped cluster Al4N2 were investigated using density functional theory (DFT) calculations. The results demonstrate that the OEEF has the capability to increase the value of the electron affinity (EA) of Al4N2 continuously and dramatically, transforming it into a member of superhalogens while maintaining its geometrical stability. Such an enhancement of the EA value of Al4N2 is attributed to the downward shift of the electronic spectrum under the effect of the OEEF. Strikingly, the relationship between the EA value of Al4N2 and the OEEF strength can be fitted by a perfect polynomial formula, which indicates that the OEEF can realize the accurate and continuous regulation of the electronic properties of Al4N2. In addition, the simulated PES of the Al4N2− cluster was observed to be blue shifted following the enhancement of the OEEF intensities, and the NLO response of the cluster can also be remarkably altered by the OEEF.