Isolated single-atom site metals/nitrogen-doped porous carbon (ISAS M/NPC, M = Fe, Co, Ni) catalysts are successfully prepared by a top-down polymerization-pyrolysis-etching-activation (PPEA) strategy, which uses dopamine as the precursor. Due to the isolated single atom Fe active sites and porous structure, the ISAS Fe/NPC catalyst displays a high benzene conversion up to 42.6% and nearly 100% phenol selectivity.