Organic hole-transporting materials (HTMs) with high hole mobility and a defect passivating ability are critical for improving the performance and stability of perovskite optoelectronics, including perovskite quantum dot light-emitting diodes (Pe-QLEDs) and perovskite solar cells. In this study, we designed two small-molecule HTMs, termed X13 and X15, incorporating the methylthio group (SMe) as defect-passivating sites to enhance the interaction between HTMs and the perovskite layer for Pe-QLED applications. Our study highlights that X15, featuring SMe groups at the para-position of the carbazole unit, demonstrates a strong interaction and superior passivation effects with perovskite quantum dots. Consequently, Pe-QLEDs (0.09 cm2) incorporating X15 as the HTM achieve a maximum external quantum efficiency (EQE) of 22.89%. Moreover, employing X15 in large-area Pe-QLEDs (1 cm2) yields an EQE of 21.10% with uniform light emission, surpassing the PTAA-based devices (EQE similar to 15.03%). Our finding provides crucial insights into the molecular design of defect-passivating small-molecule HTMs for perovskite light-emitting diodes and related optoelectronic devices.