Understanding the effect of additive on the interfacial charge-carrier transfer dynamics is very crucial to obtaining highly efficient perovskite solar cells (PSCs). Herein, we designed a simple additive, dimethyl oxalate (DO), functioning as an effective defect passivator of perovskite grain boundaries via the coordination interaction between the carbonyl (C=O) and the exposed Pb²⁺. The modification with DO produces pinhole-free and compact perovskite films, enhancing the transportation capability of carriers. As a consequence, the DO-treated PSCs exhibited a power conversion efficiency (PCE) of 22.19%, which is significantly higher than that of the control device without additive (19.58%). More importantly, detailed transient absorption characterization reveals that the use of additive can decrease the hot-carrier cooling dynamics, improve the carrier transfer, and eliminate nonradiative recombination in PSCs. This present work provides a profound understanding the additives effect on the carrier dynamics in PSCs toward the Shockley−Queisser limit.