A facile electrochemical approach was developed for controllable synthesis of ytterbium hexacyanoferrate(II) (YbHCF(II)) carambolalike microparticles. The prepared samples were characterized by XRD, EDS and SEM techniques. The composition of YbHCF(II) sample could be assigned to be KYb[Fe(CN)6]∙xH2O. By controlling the synthetic conditions, such as applied potential and deposition time, the size and surface morphology of the synthesized materials could be well controlled. The modified Au electrode by YbHCF(II) carambolalike microparticles possesses prominent electrocatalytic activity toward the reduction of hydrogen peroxide.