Porphyrin derivatives have recently emerged as hole transport layers (HTLs) because of their electron-rich characteristics. Although several successes with porphyrin-based HTLs have been recently reported, achieving excellent solar cell performance, the chances to improve this further by molecular engineering are still open. In this work, Zn porphyrin (PZn)-based HTLs were developed by conjugating fluorinated triphenylamine (FTPA) wings at the perimeter of the PZncore for low-temperature perovskite solar cells (L-PSCs). The fluorinated PZn-HTLs (PZn–2FTPA and PZn–3FTPA) exhibited superior HTL properties compared to the nonfluorinated one (PZn–TPA). Moreover, their deeper highest occupied molecular orbital energy levels were beneficial for boosting open-circuit voltages, and their enhanced face-on stacking improved the hole transport properties. The L-PSC using PZn–2FTPA achieved the highest performance of 18.85%. Thus far, this result is one of the highest reported power conversion efficiencies among the PSCs using porphyrin-based HTLs.