Although doped hole-transport materials (HTMs) offer an efficiency benefit for perovskite solar cells (PSCs), they inevitably diminish the stability. Here, we describe the use of various chlorinated small molecules, specifically fluorenone-triphenylamine (FO-TPA)-x-Cl [x = para, meta, and ortho (p, m, and o)], with different chlorine-substituent positions, as dopant-free HTMs for PSCs. These chlorinated molecules feature a symmetrical donor–acceptor–donor structure and ideal intramolecular charge transfer properties, allowing for self-dopin...