Hybrid organic–inorganic layered (2D) halide perovskites have demonstrated advantages in improving the performance and stability of perovskite solar cells, and there is an ongoing interest in tailoring organic cations for their application in photovoltaics. We apply tailored molecular systems based on perfluorinated benzylammonium (F-BNA) and 1,4-phenylenedimethylammonium (F-PDMA) cations, forming Ruddlesden–Popper and Dion–Jacobson perovskite phases, respectively, at the interface with 3D perovskite layers in conventional n–i–p perovskite solar cells. The characteristics of 2D/3D perovskite phases are investigated through a combination of techniques including X-ray diffraction, UV–vis absorption, and photoluminescence spectroscopy. We demonstrate the beneficial effects of perfluoroarene perovskite phases in improving the stability and performance toward advancing photovoltaics.