<p>For cluster catalysts, reducing their size to single atoms gives rise to precise and high-selective catalytic performance, at the cost of losing some tunability. Superatoms, the entirety with atom-like electronic shells and fine-tunable properties as clusters, are promising candidates for cluster catalysts. Here, we predicted a superatom-assembled two-dimension Al₈O₃ superatom-oxide framework (SOF) using first principles calculation, where the Al₈ core comprises two 8-electron Al₄ superatoms and further linked by oxygen atoms in a graphene-like lattice, resulting in porous and stable geometry. The Al₈O₃-SOF serves as an efficient superatomic catalyst for nitric oxide (NO) reduction reaction, where the Al₄ superatomic unit acts cohesively as the active site throughout the catalytic process and its superatomic <i>P</i> orbital plays an important role in activating NO molecule. Additionally, the catalytic activity of Al₈O₃-SOF increases when the two central Al atoms of the Al₈ core are replaced by Ga atoms, reducing the limiting potential to −0.48 V comparable to that of the reported Pt(100). Our work proposes a novel series of superatomic catalysts and reveals the superatomic behavior in the catalytic process, providing references for the development of efficient heterogeneous catalysts.</p>