Volatile solid additives (SADs) are considered as a simple yet effective approach to tune the film morphology for high-performance organic solar cells (OSCs). However, the structural effects of the SADs on the photovoltaic performance are still elusive. Herein, two volatilizable SADs were designed and synthesized. One is SAD1 with twisted conformation, while the other one is planar SAD2 with the S···O noncovalent intramolecular interactions (NIIs). The theoretical and experimental results revealed that the planar SAD2 with smaller space occupation can more easily insert between the Y6 molecules, which is beneficial to form a tighter intermolecular packing mode of Y6 after thermal treatment. As a result, the SAD2-treated OSCs exhibited less recombination loss, more balanced charge mobility, higher hole transfer rate, and more favorable morphology, resulting in a record power conversion efficiency (PCE) of 18.85% (certified PCE: 18.7%) for single-junction binary OSCs. The universality of this study shed light on understanding the conformation effects of SADs on photovoltaic performances of OSCs.