Microstructural development of ultra low C, N, Fe-Cr alloy and pure copper processed by equal-channel angular pressing (ECAP) have been examined focusing on the initial stage of the formation of ultrafine grain structure. Fe-Cr alloys were pressed at 423 K while pure copper at room temperature for 1 to 3 passes via the route Bc to compare at the equivalent homologous temperature. Microstructural evolutions were characterized by electron backscatter diffraction (EBSD) image and transmission electron microscopy (TEM). It was found that deformation structures were mostly deformation-induced subboundaries in both the materials after one pass, but the fraction of high-angle grain boundary became higher in the Fe-Cr alloys than in pure copper in subsequent passes by increasing misorientation of the boundaries. The more enhanced formation of high angle boundaries in Fe-Cr alloys was discussed in terms of the nature of crystal slip of FCC and BCC structures.