AbstractA nickel–copper alloy is prepared by using the oxalate method and subsequent in situ reduction. The bimetallic alloy is mixed with gadolinium‐doped ceria (CGO) to obtain a composite material with mixed electronic–ionic conductivity. The catalytic and electrocatalytic properties of the composite material for ethanol conversion are described. Different conditions to simulate bio‐ethanol feed operation are selected. Electrochemical tests are performed by utilizing the NiCu/CGO cermet as a barrier layer in a conventional anode‐supported solid‐oxide fuel cell (AS‐SOFC). A comparative study between the modified cell and a conventional AS‐SOFC without the protective layer is made. A maximum power density of 277 mW cm−2@0.63 V is recorded in the presence of a mixture of ethanol–water for a cell containing the protective anodic layer compared with 231 mW cm−2@0.64 V for a bare cell under the same conditions. This corresponds to a 20 % increase in performance.