AbstractDespite considerable development in performance, both poor operational stability and high costs associated with hole conductors such as 2,2′,7,7′‐tetrakis[N,N‐di(4‐methoxyphenyl)amino]‐9,9′‐spirobifluorene (spiro‐OMeTAD) and Poly[bis(4‐phenyl)(2,4,6‐trimethylphenyl)amine (PTAA) of perovskite solar cells (PSCs) need to be addressed by the research community. Here, two nonspiro hole transporting materials (HTMs), namely HTM‐1 and HTM‐2, are designed and straightforwardly synthesized exhibiting remarkable electrochemical properties and hole mobilities. In particular, the PSC based on the methoxy derivative (HTM‐2) exhibits a remarkable efficiency of 21.2% (stabilized efficiency of 20.8%), which is superior to the benchmark HTM spiro‐OMeTAD (stabilized efficiency of 20.4%). These results establish that the molecular design is effective in improving the performance of PSCs. Importantly, these two HTMs show admissible long‐term stability under different harsh conditions such as thermal stress up to 85 °C, high humidity level of 60% ± 10%, and continuous illumination over 1000 h. These insights allow correlating the impact of molecular design on optoelectronic properties of nonspiro‐based hole conductors with the overall device performance.