The effect of minor element additions (Ca, Al) on microstructural change and magnetic properties of Fe-Nb-Cu-Si-B alloy has been investigated, in this paper. The Fe-Si-B-Nb-Cu(-Ca-Al) alloys were prepared by arc melting in argon gas atmosphere. The alloy ribbons were fabricated by melt-spinning, and heat-treated under a nitrogen atmosphere at 520-570^oC for 1 h. The soft magnetic properties of the ribbon core were analyzed using the AC B-H meter. A differential scanning calorimetry (DSC) was used to examine the crystallization behavior of the amorphous alloy ribbon. The microstructure was observed by X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscope (SEM). The addition of Ca increased the electrical resistivity to reduce the eddy current loss. And the addition of Al decreased the intrinsic magnetocrystalline anisotropy K1 resulting in the increased permeability. The reduction in the size of the α-Fe precipitates was observed in the alloys containing of Ca and Al. Based on the results, it can be concluded that the additions of Ca and Al notably improved the soft magnetic properties such as permeability, coercivity and core loss in the Fe-Nb-Cu-Si-B base nanocrystalline alloys.