A facile and novel processable method to synthesize the Ni nanoparticles (Ni NPs) by tailoring their size in the matrix of the silicon oxycarbide (SiOC) ceramic system is reported. This method is based on polymer‐derived ceramics (PDCs), instead of the conventional powder route. The specific structural characteristics and magnetic properties of the various Ni NPs/SiOC composites as a function of carbon content are systematically investigated. The magnetic properties are experimentally investigated as a function of NP size and measurement temperature. It is demonstrated that the change in the size of Ni NPs (average from ≈4 to ≈ 19 nm) determines the magnetic nature of superparamagnetism. Zero‐field‐cooled (ZFC) and field‐cooled (FC) magnetization studies under magnetic fields of 100 Oe are performed. The saturated M versus H (M–H) loops (saturation magnetization) increase and the coercivity decreases with the size reduction of Ni NPs. It is an indicator of the presence of superparamagnetic behavior and single‐domain NP for ceramic materials.