Complex concentrated alloys (CCAs) with a face-centered-cubic (FCC) structure exhibit remarkable mechanical properties, introducing the expansion of compositional space in alloy design for structural materials. The formation of a single solid-solution phase is enabled by configuring various 3d-transition elements, while doping other elements even of a small portion generally leads to the formation of brittle intermetallic compounds. Herein, we demonstrate through a systematic investigation of single FCC (CoNi)100-xMox alloys that a wide range of refractory element Mo can simultaneously improve the strength and ductility while sustaining the solid-solution structure. The addition of Mo with a larger atomic size than those of 3d-transition elements introduces severe lattice distortion in the FCC lattice and causes grain-boundary segregation enriched by Mo atoms. In addition, increasing Mo content effectively reduces the stacking fault energy (SFE). The increased lattice distortion with Mo content enhances the solid-solution strengthening of the alloys. Besides, along with reduced SFE and stabilization of the dislocation emission site by grain-boundary segregation, this elevated solid-solution strengthening increases grain-boundary strengthening, reaching a yield strength of ∼1 GPa. Moreover, the reduction of SFE with increasing Mo results in the transition of dislocation substructures and the refinement of deformation twins, allowing for enhanced strain-hardening capability and thus ∼1.3 GPa tensile strength and ∼50% ductility. Such compositive and synergetic effects of refractory element Mo enable the CCAs with a single FCC solid solution to overcome the strength and ductility trade-off.@en