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Protonic ceramic ethane fuel cells fed by hydrocarbon fuels are demonstrated to be effective energy conversion devices. However, their practical application is impeded by a lack of anode materials combining excellent catalytic activity with good chemical stability and anti‐carbon deposition properties. In this work, in which Sr2Fe1.5Mo0.5O6‐δ (SFM) double perovskite oxide is used as the matrix framework, catalytic activity toward H2 and C2H6 oxidation is systematically investigated using Ba‐doping. It is found that the concentration of the oxygen vacancy is gradually improved with increased Ba content to significantly enhance catalytic activity toward H2 and C2H6 oxidation. From the series studied, Ba0.6Sr1.4Fe1.5Mo0.5O6‐δ exhibits the highest catalytic activity, while the power densities of the electrolyte‐supported Ba0.6SFM/BaCe0.7Zr0.1Y0.2O3‐δ (BCZY)/La0.58Sr0.4Co0.2Fe0.8O3‐δ (LSCF)‐Sm0.2Ce0.8O2‐δ (SDC) single cell reach 205 and 138 mW cm–2 at 750°C in H2 and C2H6, respectively. The ethane conversion rate of the experimental cell is shown to reach 38.4%, while simultaneously maintaining ethylene selectivity at 95%. Furthermore, the single cell exhibits no significant attenuation during stable operation for 20 h, as well as demonstrating excellent anti‐coking performance. The proposed results suggest that Ba0.6Sr1.4Fe1.5Mo0.5O6‐δ represents a promising anode material for efficient hydrocarbon‐related electrochemical conversion to realize the coproduction of ethylene and power in protonic ceramic ethane fuel cells. [ABSTRACT FROM AUTHOR]