The approach to catheter-based radiofrequency ablation of atrial fibrillation has evolved, and as a consequence, more energy is delivered in the posterior left atrium, exposing neighboring tissue to untoward thermal injury. Simultaneously, catheter technology has advanced to allow more efficient energy delivery into the myocardium, which compounds the likelihood of collateral injury. This review focuses on the basic principles of thermodynamics as they apply to energy delivery during radiofrequency ablation. These principles can be used to titrate energy delivery and plan ablative approaches in an effort to minimize complications during the procedure.