Dopant‐Free Small‐Molecule Hole‐Transporting Material for Inverted Perovskite Solar Cells with Efficiency Exceeding 21%

: Hole-transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long-term stability, high-performance dopant-free small-molecule HTMs (SM-HTMs) are greatly desired. However, such dopant-free SM-HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor-acceptor-type SM-HTMs (MPA-BTI and MPA-BTTI) are devised, which synergistically integrate several design principles for high-performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant-free MPA-BTTI-based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long-term stability under illumination, which breaks the long-time standing bottleneck in the development of dopant-free SM-HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well-aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA-BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high-performance dopant-free SM-HTMs in PVSCs.