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This invention relates to the field of electrode technology, and more particularly to symmetrical composite electrodes, their preparation methods, and applications. This invention utilizes a one-pot method for self-assembly of doped cubic lanthanum ferrite-based perovskite oxide and doped cubic fluorite-type cerium oxide, followed by in-situ precipitation of doped metal nanoparticles. The chemical formula of the doped cubic lanthanum ferrite-based perovskite is (La... 0.5 Sr 0.5 )[(Fe 0.9 Nb 0.1 ) 1.0‑x M x ]O 3‑δ The chemical formula of doped fluorite-type cerium oxide is Gd. 0.075 Ce 0.925‑y M y O 2‑δ The doped metal nanoparticles are elemental M. When a reducing gas is introduced, the metal nanoparticles M precipitate in situ. This heterogeneous structure of the metal particles is tightly bonded to the composite electrode material, exhibiting good dispersion, and the embedded structure ensures excellent electrode stability. As a symmetrical electrode for SOEC, this invention achieves superior catalytic activity for carbon dioxide reduction and methanol oxidation.