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Background Anterior–posterior electrode placement is preferred in electrical cardioversion of atrial fibrillation. However, the optimal anterior–posterior electrode position in relation to the heart is not studied. Methods and Results We performed a prospective observational study on patients presenting for cardioversion of atrial fibrillation. Electrodes were placed in the anterior–posterior position and shock was delivered in a step‐up approach (100 J→200 J→360 J). Fluoroscopic images were obtained, and distances were measured from points A, midanterior electrode; and B, midposterior electrode, to midpoint of the cardiac silhouette. Patients requiring one 100 J shock for cardioversion success (group I) were compared with those requiring >1 shock/100 J (group II). Logistic regression was used to determine the impact of electrode distance on low energy (100 J) cardioversion success. Computed tomography scans from this cohort were analyzed for anatomic landmark correlation to the cardiac silhouette. Of the 87 patients included, 54 (62%) comprised group I and 33 (38%) group II. Group I had significantly lower distances from the mid–cardiac silhouette to points A (5.0±2.4 versus 7.4±3.3 cm; P