Perovskite solar cells (PSCs) have recently achieved over 26% power conversion efficiency, challenging the dominance of silicon-based alternatives. This progress is significantly driven by innovations in hole transport materials (HTMs), which notably influence the efficiency and stability of PSCs. However, conventional organic HTMs like PTAA, although highly efficient, suffer from thermal degradation, moisture ingress, and high cost. This study explores the potential of iminodibenzyl, a moiety known for its strong electron-donating capabilities in pharmaceutical applications, as a novel HTM. A series of fluorene-based derivatives incorporating iminodibenzyl (TMF-2 and TDF-2) and diphenylamine (TMF-1 and TDF-1) units were synthesized and characterized. The new HTMs demonstrated commendable optical, electrochemical, and thermal properties, as well as enhanced photostability. Among them, TDF-2 achieved a power conversion efficiency (PCE) of 19.38%, the highest of the new materials. Although these efficiencies are slightly lower than the benchmark PTAA (20.20%), the study underscores the potential of iminodibenzyl to enhance photostability and increase HOMO levels, making it a promising candidate for future HTM development in PSCs.