To study the relationship between brain network and shooting performance during shooting aiming, we collected electroencephalogram (EEG) signals from 40 skilled shooters during rifle shooting and calculated the EEG functional coupling, functional brain network topology, and correlation coefficients between these EEG characteristics and shooting performance. Our result shows a significant negative correlation between shooting performance and functional coupling between the prefrontal, frontal, and temporal regions of the right brain in the Beta1 and Beta2 frequency bands. Global and local brain network topology characteristics were also significantly correlated with shooting performance. These findings indicate that under these experimental conditions, shooters with higher shooting performances exhibit lower functional coupling, higher global, and lower local information integration efficiency during shooting. These conclusions may provide a theoretical basis of the EEG brain network for studying the mental status of shooters while shooting.