Li-TFSI/t-BP system is essential for doping hole-transporting layer (HTL) to construct efficient perovskite solar cells (PSCs). However, the hygroscopicity and Li+ migration of Li-TFSI, as well as the corrosiveness and volatility of t-BP, can have negative impacts on the efficiency and stability of PSCs. Herein, a novel non-ionic fluorinated p-dopant 1-[bis (trifluoromethanesulfonyl) methyl]-2,3,4,5,6-pentafluorobenzene (PFB-TFSI) is developed to replace Li-TFSI/t-BP system. The non-ionic structure of PFB-TFSI allows it to dissolve in chlorobenzene without t-BP. Moreover, due to the lower HOMO level of PFB-TFSI, it can directly oxidize PTAA to generate [PTAA]+ radical cations without post-treatment, achieving effective doping of PTAA. The moisture resistance of HTL is also improved due to the presence of multiple fluorine atoms in PFB-TFSI. Ultimately, compared to 21.98% efficiency of PSC based on PTAA:Li-TFSI/t-BP, PSC based on PTAA:PFB-TFSI achieved higher efficiency (24.22%). Furthermore, the long-term stability of PSC based on PTAA:PFB-TFSI is greatly improved, retaining 88% of the initial efficiency after aging for 300 hours at 85 °C and 50-70% relative humidity, whereas PSC based on PTAA:Li-TFSI/t-BP only retains 63%.