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Plasma ion immersion implantation is a promising technique for nitriding. A case study of the characterization of the plasma ion immersion implantation nitriding of iron alloys is the plasma ion immersion implantation nitriding of pure Fe. A set of Fe samples of 99.98% purity and with different defect structure was plasma ion immersion implantation nitrided at different temperatures. Depth profiling of the samples was achieved using positron annihilation spectroscopy with a slow positron beam and nanoindentation. A correspondence was found between the line shape parameter S and the hardness of the plasma ion immersion implantation treated samples.