Most prosthetic myoelectric control studies have shown good performance for unimpaired subjects. However, performance is generally unacceptable for amputees. The primary problem is the poor quality of electromyography (EMG) signals of amputees compared with healthy individuals. To improve clinical performance of myoelectric control, this study explored transcranial direct current stimulation (tDCS) to modulate brain activity and enhance EMG quality. We tested six unilateral transradial amputees by applying active and sham anodal tDCS separately on two different days. Surface EMG signals were acquired from the affected and intact sides for 11 hand and wrist motions in the pre-tDCS and post-tDCS sessions. Autoregression coefficients and linear discriminant analysis classifiers were used to process the EMG data for pattern recognition of the 11 motions. For the affected side, active anodal tDCS significantly reduced the average classification error rate (CER) by 10.1%, while sham tDCS had no such effect. For the intact side, the average CER did not change on the day of sham tDCS but increased on the day of active tDCS. These results demonstrated that tDCS could modulate brain function and improve EMG-based classification performance for amputees. It has great potential in dramatically reducing the length of learning process of amputees for effectively using myoelectrically controlled multifunctional prostheses.