Fe-Si-Cr soft magnetic powder cores (SMCs), with high electrical resistivity, magnetic permeability, saturation magnetic induction, and good corrosion resistance, are widely applied to inductors, filters, choke coils, etc. However, with the development of electronic technology with high frequency and high power density, the relative decline in the magnetic properties limits the high-frequency application of SMCs. In this paper, the phosphating process and polyimide (PI) insulation coating is applied to Fe-Si-Cr SMCs to reduce the core loss, including hysteresis loss and eddy current loss. The microstructure and composition of Fe-Si-Cr powders were analyzed by SEM, XRD, and Fourier-transform infrared spectra, respectively. The structural characteristics of the Fe-Si-Cr @ phosphate layer @ PI layer core–shell double coating were studied, and the best process parameters were determined through experiments. For SMCs with 0.4 wt% content of PI, the relative permeability is greater than 68%, and the core loss is the lowest, 7086 mW/cm3; annealed at 500 °C, the relative permeability is greater than 57%, and the core loss is the lowest, 6222 mW/cm3. A 0.4 wt% content of PI, annealed at 500 °C, exhibits the ideal magnetic properties: μe = 47 H/m, P = 6222 mW/cm3. [ABSTRACT FROM AUTHOR]