Removing micropollutants in real water is a scientific challenge due to primary dissolved organic carbon (DOC) and high energy consumption of current technologies. Herein, we develop a self-purification process for the preferential destruction of various micropollutants in municipal wastewater, raw drinking water, and ultrapure water with humic acid (HA) driven by the surface microelectronic field of Fe 0 -Fe y C z /Fe x -GZIF-8-rGO without any additional input. It was verified that a strongly polar complex consisting of an electron-rich HA/DOC area and an electron-poor micropollutant area was formed between HA/DOC and micropollutants, promoting more electrons of micropollutants in the adsorbed complex to delocalizing to electron-rich Fe species area and be trapped by O 2 , which resulted in their surface cleavage and hydrolyzation preferentially. The higher micropollutant degradation efficiency observed in real wastewaters was due to the greater complex polarity of DOC. Moreover, the electron transfer process ensured the stability of the surface microelectronic field and continuous water purification. Our findings provide a new insight into low-energy combined-micropollution water treatment.