HighlightsThe first construct of a multi-field-coupled synergistic ion transport system (MSITS) in Li+extraction is proposed.Effectively suppress the ion concentration polarization effect of the ion-enrichment zone at the membrane interface.The MSITS equipped with heterogeneous membrane exhibited outstanding separation performance with Li+flux of 367.4 mmol m−2h−1and Li+/Co2+selectivity of 216,412, outperforming previous reports.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01106-5.