The effect of adding elements to promote phase separation on the functional properties of medium-entropy alloys has rarely been reported. In this paper, medium-entropy alloys with dual FCC phases were prepared by adding Cu and Ag elements, which exhibited a positive mixing enthalpy with Fe. Dual-phase Fe-based medium-entropy alloys were fabricated via water-cooled copper crucible magnetic levitation melting and copper mold suction casting. The effects of Cu and Ag elements microalloying on the microstructure and corrosion resistance of a medium-entropy alloy were studied, and an optimal composition was defined. The results show that Cu and Ag elements were enriched between the dendrites and precipitated an FCC2 phase on the FCC1 matrix. During electrochemical corrosion under PBS solutions, Cu and Ag elements formed an oxide layer on the alloy's surface, which prevented the matrix atoms from diffusing. With an increase in Cu and Ag content, the corrosion potential and the arc radius of capacitive resistance increased, while the corrosion current density decreased, indicating that corrosion resistance improved. The corrosion current density of (Fe63.3Mn14Si9.1Cr9.8C3.8)94Cu3Ag3 in PBS solution was as high as 1.357 × 10-8 A·cm-2.