• M-Nx-C active sites, particularly unconventional UM-Nx-C (x≠4), are crucial for non-radical persulfate activation in single-atom catalysts.
• Direct and indirect synthesis methods for M-Nx-C sites are systematically reviewed, with emphasis on UM-Nx-C formation.
• Catalyst supports such as g-C3N4, MOFs, COFs, and other carbon materials significantly influence the formation and performance of M-Nx-C sites.
• The review highlights the role of M-Nx-C in non-radical pathways (e.g., high-valence metals, singlet oxygen, electron transfer) for organic contaminant degradation.