HighlightsA nanofiber composite reinforced organohydrogel with multifunctionality is prepared.The composite organohydrogel possesses multiple interfacial bondings and multi-level strengthening and toughening mechanism is proposed.The composite organohydrogel exhibits long-term strain sensing stability and can be used for high performance electromagnetic interference shielding.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01148-9.