Hole-transporting materials (HTMs) are indispensable for realizing efficient and stable perovskite solar cells (PSCs). Herein, a novel dibenzo[g,p]chrysene-based HTM, termed FTPE-OSMe, is synthesized with peripheral methoxy- and methylthio-groups, which contrasts with most other small molecule HTMs that feature only methoxy-groups. The presence of methoxy- and methylthio-groups endows FTPE-OSMe with appropriate energy levels, high-hole mobility and enhanced interfacial interactions. PSCs employing Li-TFSI and 4-tert-butylpyridine-doped FTPE-OSMe demonstrate a remarkable power conversion efficiency (PCE) of 24.94% (certified 24.89%). The larger-scale PSC (1.0 cm2) and module (29.0 cm2) yield PCEs of 23.57 and 20.22%, respectively. In addition, the dopant-free FTPE-OSMe-based PSCs exhibit a respectable PCE of 22.40% and excellent stability.|A novel dibenzo[g,p]chrysene-based HTM is synthesized with peripheral methoxy- and methylthio-groups, which endow them with appropriate energy levels, high-hole mobility, and enhanced interfacial interactions. This results in a remarkable certified power conversion efficiency of 24.89% for n-i-p devices. The larger-scale PSC (1.0 cm2) and module (29.0 cm2) yield PCEs of 23.57 and 20.22%, respectively. image