The Fe-Si-B-Nb-Cu alloys containing Ca and Al were rapidly solidified to thin ribbons by melt-spinning. The ribbons were ball-milled to make powders, and then mixed with 1 wt.% water glass and 1.5 wt.% lubricant. The mixed powders were burn-off, and then compacted to form toroidal-shaped cores, which were heat treated to crystallize the nano-grain structure and to remove residual stress of material. The characteristics of the powder cores were analyzed using a differential scanning calorimetry (DSC) and a B-H meter. The microstructures were observed using transmission electron microscope (TEM). The optimized soft magnetic properties (μi and P_cv) of the powder cores were obtained from the Ca and Al containing alloys after annealing at 530 °C for 1 h. The core loss of Fe-Si-B-Nb-Cu-based powder cores was reduced by the addition of Ca element, and the initial permeability increased due to the addition of Al element.