AbstractOrganic solar cells (OSCs) have achieved remarkable power conversion efficiencies (PCEs) of over 19 % in the past few years due to the rapid development of non‐fullerene acceptors (NFAs). However, the operational stability remains a great challenge that inhibits their commercialization. Recently, oligomeric NFAs (ONFAs) have attracted great attention, which not only can deliver excellent device performance, but also improve the thermal‐/photo‐ stability of OSCs. This is attributed to the suppressed molecular diffusion of ONFAs associated with their high glass‐transition temperature (T_g) and improved thermodynamic properties of ONFAs. Herein, we focus on investigating the correction between the ONFA chemical structure, material properties, device performance, and stability. In addition, we also try to point out the challenges in synthesizing ONFAs and provide potential directions for future ONFA designs.