Knowledge of the psychophysiological responses that characterize optimal motor performance is required to inform biofeedback interventions. This experiment compared cortical, cardiac, muscular, and kinematic activity in 10 experts and 10 novices as they performed golf putts in low- and high-pressure conditions. Results revealed that in the final seconds preceding movement, experts displayed a greater reduction in heart rate and EEG theta, high-alpha, and beta power, when compared to novices. EEG high-alpha power also predicted success, with participants producing less high-alpha power in the seconds preceding putts that were holed compared to those that were missed. Increased pressure had little impact on psychophysiological activity. It was concluded that greater reductions in EEG high-alpha power during preparation for action reflect more resources being devoted to response programming, and could underlie successful accuracy-based performance.