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A button‐typed single solid oxide fuel cell (SOFC) with an internal catalytic reforming layer is tested for direct‐fed ethanol SOFC technology. This catalytic functional layer consists of 5 wt% Rh/CeZrO2 catalyst and is applied in front of conventional nickel–yttria–stabilized zirconia (Ni–YSZ) anode to convert the ethanol fuel (35 vol%) into a hydrogen‐rich gas stream via the ethanol steam reforming reaction under harsh operating conditions for 24 h (steam‐to‐carbon [S/C] ratio = 3.1, 600 °C, and weight hourly space velocity [WHSV] of 176 h−1). The X‐ray powder diffraction (XRD) analysis and transmission electron microscopy (TEM) images reveal highly dispersed Rh nanoparticles with an average size of 2 nm over CeZrO2 support. Unlike the button cell without the catalytic functional layer, the electrochemical performance of the button cell with the catalytic functional layer illustrates a high coking resistance while maintaining a good power density output. The proposed SOFC with the catalytic functional layer is a viable solution for future electric cars with bioethanol‐fed SOFC technology.