Fe_91-xZr₇Cr₂B_x (x=10, 12) and Fe₈₁Zr₇M₂B₁₀(M=Nb,W) amorphous alloys were prepared by the single roller melt-spinning and isothermally annealed at different temperatures. The thermal stability, microstructure and magnetic property of the alloys were investigated by X-ray diffraction (XRD), simultaneous thermal analysis (STA) and vibrating sample magnetometer (VSM), respectively. Research shows that the four kinds of amorphous alloys all exist three crystallization peaks in the STA curves, but have different crystallization initial products and crystallization processes. The initial crystallization product of Fe₈₁Zr₇Nb₂B₁₀alloy, which is a single α-Fe phase. The initial crystallization products of Fe₈₁Zr₇W₂B₁₀ amorphous alloy are similar to those of Fe₇₉Zr₇Cr₂B₁₂ alloy, which are α-Fe and Fe₂₃B₆ phases. The coercivity is different each other along with the change of heat treatment temperature, because of their different crystallization products. Fe₈₁Zr₇Nb₂B₁₀ alloy has low Hc after heat treatment.