The electrochemical properties of an electroactive rare earth metal hexacyanoferrate, neodymium hexacyanoferrate (NdHCF) were studied by mechanically attaching NdHCF samples to the surface of carbon ceramic electrodes (CCEs) derived from sol–gel technique. The resulting modified electrodes exhibit well-defined redox responses with the formal potential of 0.241V (versus SCE) at a scan rate of 20mVs−1 in 0.5M KCl solution. The voltammetric characteristics of the NdHCF-modified CCEs in the presence of different alkali metal cations (Li+, Na+, K+, Rb+ and Cs+) were investigated by voltammetry. The NdHCF-modified CCEs presented a good electrocatalytic activity towards the reduction of hydrogen peroxide (H2O2), and was used for amperometric detection of H2O2. In addition, the NdHCF-CCEs exhibited a distinct advantage of simple preparation, surface renewal, good stability and reproducibility.