A set of novel hole-transporting materials (HTMs) based on pi-extension through carbazole units was designed and synthesized via a facile synthetic procedure. The impact of isomeric structural linking on their optical, thermal, electrophysical, and photovoltaic properties was thoroughly investigated by combining the experimental and simulation methods. Ionization energies of HTMs were measured and found to be suitable for a triple-cation perovskite active layer ensuring efficient hole injection. New materials were successfully applied in perovskite solar cells, which yielded a promising efficiency of up to almost 18% under standard 100 mW cm(-2) global AM1.5G illumination and showed a better stability tendency outperforming that of 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene. This work provides guidance for the molecular design strategy of effective holeconducting materials for perovskite photovoltaics and similar electronic devices.