Natural nacre exhibits extraordinary functional and structural diversity, combining high strength and toughness. The mechanical properties of nacre are attributed to (i) a highly arranged hierarchical layered structure of inorganic minerals (95 vol %) containing a small amount only of organic materials (5 vol %), (ii) abundant synergistic interfacial interactions, and (iii) formation under ambient temperature. Herein, inspired by these three design principles originating from natural nacre, the supertough bioinspired graphene-based nanocomposite fibers (BGNFs) are prepared under room temperature via sequential interfacial interactions of ionic bonding and π-π interactions. The resultant synergistic effect leads to a super toughness of 18.7 MJ m-3 as well as a high tensile strength of 740.1 MPa. In addition, the electrical conductivity of these supertough BGNFs is as high as 384.3 S cm-1. They can retain almost 80% of this conductivity even after 1000 cycles of loading-unloading testing, which makes these BGNFs promising candidates for application in flexible and stable electrical devices, such as strain sensors and actuators.