A new bismuth hexacyanoferrate (BiHCF) modified carbon ceramic electrodes (CCEs) fabricated by electrodeposition was reported for the first time. The electrochemical behavior of the resulting modified electrodes was investigated by cyclic voltammetry. The BiHCF-modified CCEs presented good electrocatalytic activity toward the oxidation of hydrazine at a reduced overpotential and was used for amperometric detection of hydrazine. The diffusion coefficient (D) of hydrazine in solution and the catalytic rate constant (k cat) were also calculated by chronoamperometric experiments. In addition, the present modified electrode exhibited the advantages of simple preparation, fast response, good stability and reproducibility for hydrazine determination.