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Novel feather-like CeO₂ microstructures were achieved by a thermal decomposition approach of Ce(OH)CO₃ precursor. The Ce(OH)CO₃ was obtained from a solvothermal method employing Ce(NO₃)₃.6H₂O with C₆H${}_{12}$N₄ and C${}_{16}$H${}_{33}$(CH₃)₃NBr (CTAB) at 190${}^{\circ }$C in a water–PEG-200 mixed solution. The feather-like CeO₂ dendrite was obtained by thermal conversion of the feather-like Ce(OH)CO₃ at 650${}^{\circ }$C in air. A reasonable growth mechanism was proposed with the soft-template effect of PEG-200. The electrochemical behavior and enzyme activity of myoglobin (Mb) immobilized on CeO₂–Nafion modified glassy carbon electrode (GCE) are demonstrated by cyclic voltammetric measurements. The results indicate that CeO₂ can obviously promote the direct electron transfer between the Mb redox centers and the electrode. The Mb on CeO₂–Nafion behaves as an elegant performance on the electrochemical reduction of trichloroacetic acid (TCA) from 0.32$\mu$M to 2.28$\mu$M. The detection limit is estimated to be 0.08$\mu$M.