Significant efforts have been devoted to developing new dopant-free hole transporting materials (HTMs) for perovskite solar cells (PVSCs). Fluoranthene is one typical cyclopentene-fused polycyclic aromatic hydrocarbon with a rigid planarized structure, and thus could be an ideal building block to construct dopant-free HTMs, which have not been reported yet. Here, we report a new and simple synthetic method to prepare unreported 2,3-dicyano-fluoranthene through a Diels-Alder reaction between dibenzofulvene and tetracyanoethylene, and demonstrate that it can serve as an efficient electron-withdrawing unit for constructing donor-acceptor (D-A) type HTMs. This novel building block not only endows the resulting molecules with suitable energy levels, but also enables highly ordered and strong molecular packing in solid states, both of which could facilitate hole extraction and transport. Thus with dopant-free HTMs, impressive efficiencies of 18.03% and 17.01% which are associated with enhanced stability can be achieved based on conventional n-i-p and inverted p-i-n PVSCs respectively, outperforming most organic dopant-free HTMs reported so far.