Achieving 20.80% Efficiency in Ternary Organic Solar Cells via Suppression of Static and Dynamic Disorder

Abstract Suppressing energetic disorder represents a critical pathway toward high‐efficiency organic solar cells (OSCs). Herein, a ternary system is successfully developed to regulate the energetic disorder and enhance the photovoltaic performance of OSCs through strategic incorporation of a dimeric acceptor NVN into D18:L8‐BO host. It is demonstrated that NVN incorporation simultaneously suppresses both static and dynamic disorder. Crucially, NVN‐mediated suppression of dynamic disorder achieved through suppressing structural relaxation is identified as the dominant factor enhancing photoluminescence quantum yield (PLQY) and minimizing non‐radiative energy loss. Furthermore, NVN optimizes the double‐fibril network morphology (DFNM), induces graded vertical phase separation, and enhances molecular packing order. These morphological improvements reinforce structural regularity and mitigate static disorder. As a result, suppressed trap states, retrained energy loss, facilitated exciton dissociation, and improved charge transport are achieved in the ternary system. Owing to these synergistic effects, the D18:L8‐BO:NVN ternary OSC achieves a remarkable power conversion efficiency (PCE) of 20.80% (certified 20.39%) with enhanced operational photostability. Overall, this work underscores the fundamental importance of energetic disorder control in achieving high‐performance OSCs.