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A new dopant-free hole transporting material (HTM) 4′,4‴,4‴'',4‴''''-(adamantane-1,3,5,7-tetrayl)tetrakis(N,N-bis(4-methoxyphenyl)-[1,1′-biphenyl]-4-amine) (Ad-Ph-OMeTAD) (named FDY for short), which consists of a nonconjugated 3D bulky caged adamantane (Ad) as the core, triphenyl amines as side arms, and phenyl units as a linking bridge, is synthesized and applied in an inverted planar perovskite solar cell (PSC). As a result, the champion device with FDY as HTM yields an impressive power of conversion efficiency (PCE) of 18.69%, with J_SC = 22.42 mA cm⁻², V_OC = 1.05 V, and FF = 79.31% under standard AM 1.5G illumination, which is ca. 20% higher than that of the device based on PEDOT:PSS (only 15.41%). Notably, the stability of PSC based on FDY is much better than that of devices based on PEDOT:PSS, and the corresponding devices retain over 90% of their initial PCEs after storing for 60 days in a nitrogen glove box without any encapsulation. Even when stored in an open air condition with 50–60% relative humidity for 188 h, the retained PCE is still over 81% of its initial one. All these results demonstrate that the new design strategy by combing the bulky and nonconjugated (aliphatic) adamantane unit as the core and triphenyl amines as side arms can efficiently develop highly efficient HTMs for PSCs, which is different from the traditional way based on conjugated backbones, and it may open a new way for scientists to design small-molecule HTMs for PSCs.