Left atrium (LA) size is a well-studied predictor of atrial fibrillation (AF) recurrence after pulmonary vein isolation (PVI). Yet, there is still little agreement on the best imaging technique to size the LA, and on the most appropriate sizing parameter. Volumetric assessment of LA with three-dimensional rotational angiography (3DRA LA volume index) might be a valid alternative to the commonly used transthoracic echocardiography (TTE LA volume index). The aim of our study was to investigate whether LA volume by 3DRA at the time of PVI is able to predict the risk of atrial fibrillation recurrence. We analysed 352 consecutive patients with symptomatic paroxysmal or persistent atrial fibrillation referred for PVI to our Institution. In all patients, LA volume index (LAVI) was assessed by TTE and by 3DRA. Sinus rhythm was restored after PVI in 348 patients (99%). Average TTE-LAVI and 3DRA-LAVI were 37 ± 12 and 83 ± 18 ml/m2, respectively. At a median follow-up of 19 (12, 24) months, 27% of patients had AF recurrence after the first PVI. At the univariate analysis, persistent AF (p < 0.01), use of anti-arrhythmic drugs (AAD) (p < 0.05) and 3DRA-LAVI (p < 0.01) were significantly associated with AF recurrence. In contrast, none of the echocardiographic parameters considered, including TTE-LAVI, was associated with AF recurrence (p = 0.29). At the multivariate analysis, 3DRA-LAVI was the only independent predictor for AF recurrence (HR 1.01 [1.00–1.03], p = 0.017). Left atrial volume measured with 3DRA is superior to TTE assessment and to AF history in predicting atrial fibrillation recurrence after PVI.