Perovskite solar cells (PSCs) with n-i-p structures often utilize an organic 2,2',7,7'-tetrakis (N, N-di-p-methoxyphenyl-amine) 9,9'-spirobifluorene (spiro-OMeTAD) along with additives of lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) and tert-butylpyridine as the hole transporting layer (HTL). However, the HTL lacks stability in ambient air, and numerous defects are often present on the perovskite surface, which is not conducive to a stable and efficient PSC. Therefore, constructive strategies that simultaneously stabilize spiro-OMeTAD and passivate the perovskite surface are required. In this work, it is demonstrated that a novel ionic liquid of dimethylammonium bis(trifluoromethanesulfonyl)imide (DMATFSI) could act as a bifunctional HTL modulator in n-i-p PSCs. The addition of DMATFSI into spiro-OMeTAD can effectively stabilize the oxidized spiro-OMeTAD cation radicals through the formation of spiro-OMeTAD TFSI because of the excellent charge delocalization of the conjugated CF SO moiety within TFSI . In addition, DMA cations could move toward the perovskite from the HTL, resulting in the passivation of defects at the perovskite surface. Accordingly, a power conversion efficiency of 23.22% is achieved for PSCs with DMATFSI and LiTFSI co-doped spiro-OMeTAD. Moreover, benefiting from the improved ion migration barrier and hydrophobicity of the HTL, still retained nearly 80% of their initial power conversion efficiency after 36 days of exposure to ambient air.