Carbazole-derived self-assembled monolayers (SAMs) are promising materials for hole-extraction layer (HEL) in conventional organic photovoltaics (OPVs). Here, a SAM Cbz-2Ph derived from 3,6-diphenylcarbazole is demonstrated. The large molecular dipole moment of Cbz-2Ph allows the modulation of electrode work function to facilitate hole extraction and maximize photovoltage, thus improving the OPV performance. Additionally, the flanking aryls of Cbz-2Ph help establish CH-pi interactions for forming a dense and well-organized SAM HEL and exhibit stronger van der Waals interactions with the donor PM6 than acceptor BTP-eC9. The stronger SAM-donor interactions modulate the PM6 distribution in PM6:BTP-eC9 bulk-heterojunction film, leading to PM6 enrichment near HEL to facilitate efficient hole extraction to the ITO anode in conventional p-i-n OPVs. Consequently, binary PM6:BTP-eC9-based devices incorporating the Cbz-2Ph HEL demonstrate an impressive efficiency of 19.18%. These cells also showcase excellent operational stability, with a T80 lifetime of approximate to 1260 h at the maximum power point, over 10 times longer than those using the traditional PEDOT:PSS HEL (T80 approximate to 96 h). Furthermore, the universal applicability of Cbz-2Ph as a HEL is evident through its successful implementation in PM6:BTP-eC9:L8-BO-F-based ternary devices and PM6:BTP-eC9-based printed OPV devices, achieving a PCE of 19.30% and 16.96%, respectively.