Side-chain engineering is an effective strategy to regulate the solubility and packing behavior of organic materials. Recently, a unique strategy, so-called terminal side-chain (T-SC) engineering, has attracted much attention in the field of organic solar cells (OSCs), but there is a lack of deep understanding of the mechanism. Herein, a new noncovalently fused-ring electron acceptor (NFREA) containing two T-SCs (NoCA-5) was designed and synthesized. Introduction of T-SCs can enhance molecular rigidity and intermolecular pi-pi stacking, which is confirmed by the smaller Stokes shift value, lower reorganization free energy, and shorter pi-pi stacking distance in comparison to NoCA-1. Hence, the NoCA-5-based device exhibits a record power conversion efficiency (PCE) of 14.82 % in labs and a certified PCE of 14.5 %, resulting from a high electron mobility, a short charge-extraction time, a small Urbach energy (E-u), and a favorable phase separation.