Ultra-high twinning-induced plasticity (TWIP) steel is receiving increasing attention in the automobile industry. Self-designed Fe–19Mn–0.6C TWIP steel was subjected to reveal the relationship between microstructures, which were related to recrystallization starting/ending temperature and cold rolling. The results indicated that initial deformation twins, secondary deformation twins, and nano-twins were successively generated in rolled TWIP steel with the increase of cold rolling, deformation twins, and dislocations, as well as with the elongation of grains. The elements remained uniformly dispersed rather than agglomerated in the twin crystals and grain boundaries. The recrystallization starting temperature changes of TWIP steel were 500–525, 400–425, 400–415, and 400–410 °C at cold rolling deformations of 25%, 50%, 75%, and 88%, respectively. Furthermore, the obtained corresponding recrystallization ending temperature changes were 580–600, 530–550, 520–540, and 500–520 °C, respectively. The linear relationship between cold deformation and hardness suggests that cold rolling can increase dislocation density and thus facilitate improving the hardness of TWIP steel.