Herein, we report, for the first-time, mesoporous carbon-supported binary and ternary catalysts with different atomic ratios of Pt/MC (100), Pt–Sn/MC (50 : 50), Pt–Re/MC (50 : 50), Pt–Sn–Re/MC (80 : 10 : 10) and Pt–Sn–Re/MC (80 : 115 : 05) prepared using a co-impregnation reduction method as anode components for membraneless ethanol fuel cells (MLEFLs). Mechanistic and structural insights into binary Pt–Sn/MC, Pt–Re/MC and ternary Pt–Sn–Re/MC catalysts were obtained using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) methods. In particular, chemical characterization via cyclic voltammetry, CO stripping voltammetry and chronoamperometry indicated that Pt–Sn–Re/MC (80 : 15 : 05) had better dynamics toward ethanol oxidation than Pt–Sn–Re/MC (80 : 10 : 10), Pt–Sn/MC (50 : 50) and Pt–Re/MC (50 : 50) catalysts. In terms of the single cell performance of the prepared catalysts, Pt–Sn–Re/MC (80 : 15 : 05) (31.5 mW cm⁻²) showed a higher power density and current density than Pt–Sn–Re/MC(80 : 10 : 10), Pt–Re/MC (50 : 50) and Pt–Sn/MC (50 : 50) at room temperature. The addition of Re into the binary Pt–Sn catalyst improved its electrical performance for ethanol oxidation in a membraneless ethanol fuel cell. As a result, the ternary-based Pt–Sn–Re/MC (80 : 15 : 05) catalyst demonstrated enhanced performance compared to monometallic and bimetallic catalysts in the ethanol oxidation reaction in a membraneless fuel cell.