Psychological fatigue, including mental fatigue and burnout, is a phenomenon that psychological function cannot remain the former level of mental activity. Athletes’ response monitoring ability decreases is up for debate under mental fatigue or burnout circumstances. In Event-related potentials studies, the amplitude of error related negativity decreases. Two experiments were carried out to explore cause-effect relationships of psychological fatigue and response monitoring. The experimental data processing was based on Artificial Intelligence computing methods, including wavelet transform, gray scale transformation and other algorithms. The first experiment was done to explain mental fatigue and response monitoring, 15 participants operated continuously 60 minutes Flanker task, and then operated 15 minutes task accompanied by light music. From the results of behavioral performances, the fatigue period compared with the fatigue-free period showed significant differences, including reaction time(p=0.029) and correct rate(p=0.046). From the results of error related negativity, the amplitude of the fatigue-free period was bigger than that of the music intervention period, the latter was bigger than that of the fatigue period (p<0.001). The second experiment was done to explore burnout and response monitoring, 24 participants were separated averagely into two groups. One group was burnout group, the other group was no burnout group. They operated 15 minutes task. From the results of behavioral performances, no burnout group was better than burnout group. From the results of error related negativity, no burnout group’s amplitude was bigger than that of burnout group, but the difference was marginally significant. The conclusions are as follows: Psychological fatigue (mental fatigue and burnout) weakens athletes’ response monitoring ability, and the effect of mental fatigue is significant.