The prerequisite for commercially viable organic solar cells (OSC) is to reduce the efficiency‐stability‐cost gap. Therefore, the cost of organic materials should be reduced by minimizing the synthetic steps, yet maintaining the molecular planarity and efficiencies achieved by the fused ring acceptors (FRA). In this respect, developing non‐fused ring acceptors (NFRA) with suitable functionalization to favor conformational planarity and effective molecular packing is beneficial and cost‐effective. Presently, the power conversion efficiency (PCE) for NFRAs is around 16 %, yet lower than the 19 % achieved for FRAs. Despite their potential, a thorough understanding of the effective structural design of NFRAs is necessary for developing efficient OSCs. This article pays special attention to the molecular design concept for NFRAs developed in the last years and analyzed the approach toward materials design and efficiency improvement, an important step toward technological application.