HighlightsThe single-atom Cu species withS= 0 spin ground state in CuIII-HHTP have been fabricated.The CuIII-HHTP exhibits remarkable performance with a high urea yield of 7.780 mmol h−1g−1with the corresponding Faradaic efficiency of 23.09% at − 0.6 V (vs. RHE).Low spin state and empty (\documentclass[12pt]{minimal}
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				\begin{document}$${d}_{{{\text{x}}^{2}\text{-y}}^{2}}^{0}$$\end{document}dx2-y20) orbitals are favorable to enhance the production urea of C–N coupling process.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01127-0.