This paper presents the relationship between the chemical composition and size of steel balls, the parameters of the nitriding process, and their magnetic properties, defined in this study by ferromagnetic resonance (FMR) and SQUID. Balls made from AISI 1010 and AISI 52100 steels, with diameters of 2.5 and 3 mm, respectively, were investigated. On samples made of AISI 1010 and AISI 52100 steel, single-phase layers of iron nitrides γ’ with a thickness of gmp = 50 and 37 μm, respectively, were produced. Then, the samples were annealed at a temperature of 520 °C for 4 h in an inert atmosphere (N2/Ar) at a pressure of 200 Pa. After the nitriding processes, steel balls were subjected to standard physical metallurgy and X-ray examinations. During annealing of nitrided layers with a two-phase layer of iron nitrides, at first, the transformation of the ε phase into the γ’ phase with the release of nitrogen into the atmosphere takes place. The FMR signals did not originate from isolated ions, but from more magnetically complex systems, e.g., Fe–Fe pairs or iron clusters, while the observed FMR line position is normally even lower and occurs for a magnetic induction below 200 mT. The fact that the magnetic centers did not contain mainly isolated Fe ions, additionally confirmed the abnormal increase in resonance signal intensity as a function of temperature, which is a behavior inconsistent with the Curie–Weiss law. The results obtained from measurements by the SQUID method, recording variations in magnetization as a function of temperature, confirm the untypical reinforcement of the magnetic conditions of the samples with the increase in temperature. For the samples tested, the magnetization was relatively weaker when the tests were conducted in a stronger magnetic field.