Fe50Cr50 metastable alloys were prepared by the mechanical alloying method with milling periods of 1, 2, 4, 6, 12 and 24 hours, respectively. The structural evolution was analyzed by the extended x-ray absorption fine structure (EXAFS). In this work, the EXAFS analysis provided the local structural information around Fe central atom. The saturation magnetization was also measured by VSM. The magnetization decreased as the process mechanical alloying progressed. The magnetic property was related to the local structural variation as a function of processing time. The analysis showed that the diffusion Cr atoms into Fe clusters caused the reduction of magnetization. EXAFS analysis exhibited that the local ordering of magnetic atoms caused the magnetic ordering. Also, EXAFS analysis showed that the long range order of Fe atoms was destroyed completely in 24 hour milling.