This study investigated the influence of competitive state on cerebral cortex activity of professional shooters with 10 m air rifle before shooting. Generally, professional athletes have higher neural efficiency compared with ordinary people. We recruited 11 national shooters to complete 60 shots under both noncompetitive and competitive shooting conditions, and simultaneously collected their electroencephalogram (EEG) and electrocardiogram (ECG) information. Theta, alpha, and beta power were computed in the last three seconds preceding each shot from average-reference 29-channel EEG, while EEG characteristics under two conditions were analyzed. The results showed a significant linear correlation between shooting accuracy and EEG power of anterior frontal, central, temporal, and occipital regions in beta and theta bands. In addition, the theta power in occipital regions, alpha power in frontal-central and left occipital regions, and beta power in frontal and mid-occipital regions were higher than those in noncompetitive state. However, heart rate (HR) and shooting accuracy did not change significantly under the two conditions. These findings reveal the changes of cortical activity underlying competition shooting as well as providing further understanding of the neural mechanisms of the shooting process and lay a foundation for the subsequent neuromodulation research.