Thermosetting organic resins are widely applied as insulating coatings for soft magnetic powder cores (SMPCs) because of their high electrical resistivity. However, their poor thermal stability and thermal decomposition lead to a decrease in electrical resistivity, thus limiting the annealing temperature of SMPCs. The large amount of internal stress generated by soft magnetic composites during pressing must be mitigated at high temperatures; therefore, it is especially important to find organic resins with excellent thermal stabilities. In this study, we prepared SMPCs using poly-silicon-containing arylacetylene resin, an organic resin resistant to high temperatures, as an insulating layer. With 2 wt % PSA as an insulating layer and annealed at 700 °C for 1 h, the FeSiAl SMPCs achieved the best magnetic properties, including the lowest core loss of 184 mW/cm³ (measured at 0.1 T and 50 kHz) and highest permeability of 96.