This report describes the development and the optimization of new synthesis routes yielding electrocatalysts for the oxygen reduction reaction (ORR) aimed at application in proton exchange membrane fuel cells (PEMFCs). The preparation protocols consist in the synthesis of two groups of hybrid inorganic-organic precursors, characterized by a different concentration of nitrogen, which subsequently undergo a high-temperature pyrolysis in inert atmosphere, washing and activation. The resulting materials show a well-controlled stoichiometry. The nitrogen incorporated in the support transforms the matrix into a supramolecular ligand, and stabilizes the electrocatalyst by coordinating the active metal clusters. The latter are composed of an "active metal" such as Pt or Pd, combined with one or more "co-catalyst" elements such as Au, Fe, Co and Ni. An extensive characterization of the carbon nitride electrocatalysts under the chemical, structural, morphological and electrochemical points of view is described, together with their use in membrane electrode assemblies (MEAs) tested in single fuel cells under operative conditions. Results indicated that the best electrocatalysts are those characterized by a "core-shell" morphology. These systems consist of metal carbon nitride materials with a low concentration of nitrogen (shell) supported on electronically conductive graphite nanoparticles (core). Promising results were obtained both in terms of ORR overpotential (eta) and of mass activity (A(m)). Indeed, eta resulted up to similar to 30 mV lower with respect to reference Pt-based systems, and an A(m), equal to 0.3-0.4g of Pd or Pt to achieve 1 kW was reached. (C) 2010 Elsevier Ltd. All rights reserved.