The typical thickness of the photoactive layer in organic solar cells (OSCs) is around 100 nm, which limits the absorption efficiency of the incident light and the power conversion efficiency (PCE) of OSCs. Therefore, light‐trapping schemes to reduce the optical losses in the thin photoactive layers are critically important for efficient OSCs. Herein, light‐trapping and electron‐collection dual‐functional small organic molecules, N,N,N′,N′‐tetraphenyloxalamide (TPEA) and N,N,N′,N′‐tetraphenylmalonamide (TPMA), are designed and synthesized by a one‐step acylation reaction. Driven by strong intermolecular force, TPEA and TPMA tend to self‐aggregate into hemispherical light‐trapping nanodots on the photoactive layer, resulting in enhanced light harvesting. Meanwhile, TPEA and TPMA demonstrate high electron mobility and excellent electron‐collection ability. Compared with the device without cathode buffer layer (CBL, PCE = 14.09%), PM6:BTP‐eC9 based OSCs with TPEA and TPMA light‐trapping CBLs demonstrate greatly enhanced PCE of 16.21% and 17.85%, respectively. Furthermore, a record PCE of 19.02% can be achieved for PM6:BTP‐eC9:PC71BM based ternary OSC with TPMA light‐trapping CBL. Moreover, TPMA exhibits a low synthesis cost of only 0.61 $ g−1 with high yield. These findings could open a window for the rational design of multifunctional CBLs for efficient and stable OSCs.