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The preparation of Ni-Mn-Ga and Ni-Mn-Ga-Fe master alloy ingots and microwires was completed by high vacuum electric furnace melt melting furnace and melt drawing liquid forming equipment, and the lattice dislocations and defects formed inside the microwires during the preparation process were corrected by stepwise ordered heat treatment. The micro-structure and phase structure were characterized using a SEM field emission scanning electron microscopy and an XRD diffractometer combined with an EDS energy spectrum analyzer; the martensitic phase transformation process of the microwires was analyzed using a DSC differential scanning calorimeter; and the superelasticity of the microwires was tested by a Q800 dynamic mechanical analyzer. The results indicate that Fe doping can refine the grain, transform the phase structure from parent phase to single 7M martensite, reduce the number of martensitic variants, and increase the mobility of the twin grain boundary interface. The MT phase transition temperature (MS) is substantially increased in the martensite transition (MT) process by the increase of the number of free electrons in its lattice. During the superelasticity (SE) test, both microwires displayed superior recover-ability of SE curves, and the Fe doping curves showed similar characteristics of “linear superelasticity”, showing higher critical stress values and complete SE in the experiment. The critical stress satisfies the Clausius-Clapeyron equation and exhibits higher temperature sensitivity than Ni-Mn-Ga microwires.