The microstructure and magnetic properties of$ Fe_{87}Zr_7Si_4B_2$ nanocrystalline alloys were studied by magnetization measurements and M ssbauer spectrometry over a wide temperature range. Three well resolved spectral components have been found and attributed to bcc-Fe grains (with almost pure iron structure), residual amorphous matrix enriched with solute elements and interfaces formed at the grain-matrix boundaries. It has been shown that, contrary to the expectation, during crystallization the atomic segregation occurs leading to the formation of primary bcc-Fe grains and the partition of Si atoms into the residual amorphous matrix.