The development of non-invasive tools able to provide valuable information about the effectiveness of a shock in external electrical cardioversion (ECV) is clinically relevant to enhance these protocols in the treatment of atrial fibrillation (AF). The present contribution analyzes the ability of a non-linear regularity index, such as sample entropy (SampEn), to follow-up noninvasively AF organization under successive attempts of ECV and to predict the effectiveness of every single shock. Results showed that, after each unsuccessful shock, a SampEn relative decrease was observed for the patients who finally reverted to normal sinus rhythm (NSR), but the largest variation took place after the first attempt, thus indicating that this shock plays the most important role in the procedure. Indeed, by considering jointly the patients who needed only one shock and the patients who needed several shocks, 91.67% (22 out of 24) of ECVs resulting in NSR, 93.55% (29 out of 31) of ECVs relapsing to AF during the first month and 100% (10 out of 10) of ECVs in which NSR was not restored were correctly classified. As conclusion, AF organization analysis via SampEn from the surface ECG can provide useful information that could improve the effectiveness of conventional external ECV protocols used in AF treatment.