Atrial fibrillation (AF) management has historically relied on thermal ablation modalities—radiofrequency (RF) and cryoballoon—which have established a high benchmark for pulmonary vein isolation (PVI). However, the inherent risk of collateral thermal injury and lesion inconsistency has driven the search for alternative energy sources. The recent clinical adoption of pulsed-field ablation (PFA), based on irreversible electroporation, represents a significant technological evolution. This narrative review provides a critical appraisal of the transition from thermal to pulsed-field technologies. We synthesized data from pivotal trials and recent health-economic analyses to evaluate the biophysical mechanisms, clinical efficacy, and safety profiles of contemporary devices. We conduct a head-to-head comparison of all modalities regarding critical safety endpoints (esophageal, neurological, and vascular), real-world procedural challenges (anesthesia, lesion assessment), and economic sustainability. While PFA offers distinct advantages in procedural speed and tissue selectivity, we highlight that thermal modalities—particularly cryoballoon and very-high-power RF—retain competitive profiles in terms of cost-effectiveness and established long-term durability. This review aims to provide a balanced roadmap for clinicians navigating the complex choice between established thermal efficacy and the promising, yet evolving, landscape of electroporation.