Organic hole-transporting materials (HTMs) based on the Ullazine core yield so far only moderate power conversion efficiencies of up to 13.08% in perovskite solar cells (PSCs). Aiming to fabricate efficient and stable PSCs, novel Ullazine derivatives bearing thiophene units were designed and synthesized, allowing modulation of the electronic states of the HTMs and further providing defect passivation ofthe perovskite surface. Experimental and theoretical analysis show that thiophene units with -N(p-MeOC6H4)(2) groups improve the conductivity of Ullazine HTMs, boosting the efficiency of PSCs to 20.21%. This value is the highest reported to date for Ullazine-based HTMs, and is close to the performance of Spiro-OMeTAD. In addition, unencapsulated PSCs based on the champion Ullazine exhibit superior stability with respect to Spiro-OMeTAD, retaining nearly 90% of the initial efficiency following 1000 h aging, which is ascribed to a combination of higher water repellency and passivation of defects on the perovskite surface. This work demonstrates the high potential of HTMs based on Ullazine core as substitutes to Spiro-OMeTAD.