The study designs and synthesizes non‐planar, propeller‐shaped hexaarylbenzene‐type (HAB) compound K5‐36 and hexa‐peri‐hexabenzocoronene (HBC)‐based K5‐13 (with a cyclized core), as cost‐effective and high‐yielding hole selective layers (HSLs) for perovskite solar cells (PSC). Using a p–i–n device structure with ITO/4PADCB/HAB or HBC (with or without)/perovskite/PDADI/PC61BM/BCP/Ag, the interaction is investigated between the synthesized materials and self‐assembled monolayer (4PADCB) elucidating mechanisms influencing the growth of wide bandgap Cs0.18FA0.82Pb(I0.8Br0.2)3 perovskite. K5‐36 facilitates the growth of wide perovskite films with larger grains and lower defect density, while promoting energy level alignment at the HSL/perovskite interface. These modifications effectively suppressed non‐radiative recombination, resulting in a higher open‐circuit voltage of 1.2V and a power conversion efficiency (PCE) exceeding 20% under AM 1.5G conditions. Under 3000K LED (1000 lux) illumination, the PCE of 4PADCB/K5‐36‐based PSCs significantly increased from 38.02 ± 0.38% (4PADCB PSC) to 41.80 ± 0.57%. Moreover, PSCs incorporating 4PADCB/K5‐36‐ and 4PADCB/K5‐13‐ demonstrate exceptional stability, retaining ≈88.5% and 98.2% of their initial PCE after 70 days of storage in a glove box. These findings highlight the potential of polyarene‐based HSLs as a promising approach for improving PSC efficiency and stability.