Here, a straightforward fabrication method to produce graphene oxide (GO) fibers liquid crystal (LC) dispersion using trivalent cation salts as ionic binder is presented. The multivalent metal cations aid in coagulating GO liquid crystalline dispersions on the fiber structures. To utilize the full potential of GO fiber, it is critically important to control the microstructure of fiber. The microstructure of GO fibers, such as shape and d-spacing between sheets, is ultimately controlled by the metal cation coagulants. Compared to divalent cations, the fast diffusion of trivalent cations induces highly dense structures. The modulation of chemical interactions and induced cross-linking by trivalent metal cations is advantageous in improving the mechanical properties of GO fibers. The increased interlayer attraction due to trivalent cation binders results in mechanically stable fibers that exhibit tensile strength and Young's modulus as high as 486 MPa and 81 GPa, respectively.