Hexakis(hexyloxy)triphenylene (HAT6) discotic liquid crystal is employed as a transparent hole-transporting material (HTM) for perovskite solar cells (PSCs) and a power conversion efficiency (PCE) of 15.7% is obtained, which is the highest using HAT6 type of HTMs. Despite lower PCE than spiro-OMeTAD-based devices (20.3%), the PSCs based on HAT6 exhibit much higher ambient and thermal stability. A fused polyaromatic core with six alkyl chains leads to high hydrophobicity, and the pi-stacked molecular columns of the HAT6 shield the bis(trifluoromethane)sulfonamide lithium salt dopant migration into the perovskite absorber. The PSCs (under N-2 condition) exhibit superior stability compared to the devices employing spiro-OMeTAD, retaining nearly 92% of their initial efficiency after 1200 h operation. Under ambient conditions, HAT6-based hole-transportation layer devices retain 93% of the initial efficiency for 690 h. Under continuous thermal stress of 85 degrees C, the devices based on HAT6 retain 95% of the initial PCE. The results demonstrate the time applicability of liquid crystal for stable PSCs fabrication.