Abstract Developing high‐performance nanofluidic fibers with synergetic ionic and electric conductivities is promising for human–machine interface interaction. In such a scenario, inter‐ and intra‐forces in constituent flakes are recognized as crucial factors in determining the derived nanofluidic fiber performance. In this work, the rheological properties of Ti 3 C 2 T x MXene solution are systematically optimized by regulating the electrostatic interaction via introducing multivalent metal cations. As a result, such multivalent cations trigger ionic crosslinking and remarkably strengthen the interaction force between nanosheets, which even forms into a tight fiber‐shaped gel network. A series of cations, such as K + , Na + , Mg 2+ , Zn 2+ , and Al 3+ , are introduced to enhance the ionic cross‐linking between interconnected flakes. The thus‐prepared Zn 2+ ‐Ti 3 C 2 T x fiber exhibits a remarkable electrical conductivity of 11 200 S cm −1 , a tensile strength of 252 MPa, and an ionic conductivity of 2.51 × 10 −3 S cm −1 . This multivalent cation crosslinking strategy could offer some insights into developing functional nanofluidic fibers for wearable or healthcare applications.