Developing dopant-free hole-transporting materials (HTMs) for high-performance perovskite solar cells (PVSCs) has been a very active research topic in recent years since HTMs play a critical role in optimizing interfacial charge carrier kinetics and in turn determining device performance. Here, a novel dendritic engineering strategy is first utilized to design HTMs with a D-A type molecular framework, and diphenylamine and/or carbazole is selected as the building block for constructing dendrons. All HTMs show good thermal stability and excellent film morphology, and the key optoelectronic properties could be fine-tuned by varying the dendron structure. Among them, MPA-Cz-BTI and MCz-Cz-BTI exhibit an improved interfacial contact with the perovskite active layer, and non-radiative recombination loss and charge transport loss can be effectively suppressed. Consequently, high power conversion efficiencies (PCEs) of 20.8% and 21.35% are achieved for MPA-Cz-BTI and MCz-Cz-BTI based devices, respectively, accompanied by excellent long-term storage stability. More encouragingly, ultrahigh fill factors of 85.2% and 83.5% are recorded for both devices, which are among the highest values reported to date. This work demonstrates the great potential of dendritic materials as a new type of dopant-free HTMs for high-performance PVSCs with excellent FF.