The purpose of this study was to examine whether variability in gaze behavior and cortical activation would differentiate expert (n = 12) and nonexpert (n = 13) small-bore rifle shooters. Spectral-activity and eye-movement data were collected concurrently during the course of a regulation indoor sequence of 40 shots from the standing position. Experts exhibited significantly superior shooting performance, as well as a significantly longer quiet eye period preceding shot execution than did nonexperts. Additionally, expertise interacted with hemispheric activation levels: Experts demonstrated a significant increase in left-hemisphere alpha and beta power, accompanied by a reduction in right-hemisphere alpha and beta power, during the preparatory period just prior to the shot. Nonexperts exhibited similar hemispheric asymmetry, but to a lesser extent than did experts. Findings suggest systematic expertise-related differences in ocular and cortical activity during the preparatory phase leading up to the trigger pull that reflects more optimal organization of the neural structures needed to achieve high-level performance.