Lead pentacyanonitrosylferrate (PbPCNF), a new Prussian blue analog, was immobilized on the surface of a carbon ceramic electrode (CCE) prepared by sol-gel method. The immobilization process consists of adding a certain amount of metallic lead to the electrode matrix before gelation, and chemical derivatization of Pb on the electrode surface to a PbPCNF solid film by immersing the electrode in a solution of sodium pentacyanonitrosylferrate (PCNF). The composition of the synthesized PbPCNF was characterized by FTIR, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) techniques. The resulting modified electrode showed electroactivity at two redox centers. The electrochemical behavior of the PbPCNF modified carbon ceramic electrode (PbPCNF j CCE) was studied by cyclic voltammetry. Under optimized conditions the peak-to-peak separation is only 39 mV, indicative of a surface reaction. Ion effects of the supporting electrolyte suggest that cations have a considerable effect on the electrochemical behavior of the modified electrode. The transfer coefficient (a) and the charge transfer rate constant at the modifying film j electrode interface (k s ) were calculated. The electrocatalytic activity of the modified electrode toward the electro-reduction of peroxodisulfate was studied in details.