We have elucidated a degradation mechanism of CrN/SiCN nanocomposite coatings by annealing at high temperature: when Fe atoms diffuse into the CrN/SiCN coatings, decomposition of a-SiCN phases arise and result in remarkable grain growth of CrN nano-crystalline. By the series of these reactions, the hardness and oxidation resistance of the coatings deteriorate remarkably. From the view point of Gibbs free energy of reaction for the formation of metal carbides, an element has been found out that can retard the decomposition of a-SiCN phases.