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Zirconium silicon nitride thin films with 1.6% Si addition were deposited via reactive magnetron sputtering and characterized by RBS, SEM-FEG, GAXRD, XPS and high temperature oxidation tests, aiming to investigate how silicon is structurally inserted in Zirconium nitride (ZrN) matrix. GAXRD results show a reduction in lattice parameter and grain size due to Si incorporation and XPS analyses demonstrate Si is present only in nitride form. Such observations proved the non-formation of substitutional or interstitial solid solution in ZrN, but the presence of Si 3 N 4 , even in low Si concentrations.