To obtain advanced quality pure copper, the microstructure of solidified copper was optimized by imposing electric pulse on liquid copper in this study. Experiments were performed to determine the effect of electric pulse voltage, arrangement mode of electrodes, and energy input on the microstructure of solidified copper. The results show that, when the energy input of electric pulse is bigger than 28.95 kJ per ton copper, the percent of fine grains increases noticeably with the increase of energy input; but when the energy input of electric pulse is smaller than 28.95 kJ per ton copper, the percent of fine grains decreases with the increase of energy input. The influence order of above factors on grain refinement is electric pulse voltage > arrangement mode of electrodes > energy input. According to the above experimental results, the optimum process conditions are chosen as the voltage being 400 V and the energy input greater than 28.95 kJ per ton copper. Meanwhile, the best arrangement mode of electrodes should be that, one electrode is immerged in the middle of liquid copper in the crystallizer, and the other is connected to the inner wall of the crystallizer, which is divided into two electrode poles for the symmetrical electric field distribution.