Attention is the most important psychological factor affecting shooting performance. The wavelet packet energy analysis method was used to explore the differences in EEG characteristics and brain activity between experts and novices while aiming and shooting in real shooting environments. Results show that the frontal and occipital regions of novices were more active when they were aiming, while the frontal, central, and occipital regions of experts were more active when they were shooting. Overall, the frontal, central, and occipital regions of novices were more active (p < 0.05), whereas for experts, it was the frontal, central, parietal, and occipital regions that were more active (p < 0.05). Brain activity was mainly concentrated in the left hemisphere of the brain for experts, indicating that they began to take action when aiming and had higher neural efficiency. This study can help the selection and training of personnel for typical tasks that require attention by monitoring and analyzing the EEG signals of operators of different skill levels.