Engineering the energetics of perovskite solar cells through the introduction of surface dipoles that assist with charge carrier extraction is a promising route to enhance the device performance without altering other device layers or fabrication parameters. In this work, we introduce four different derivatives of dicationic phosphonium-bridged ladder stilbenes (PYMC) in inverted perovskite solar cells with the device structure of ITO/Meo-2pacz/perovskite/PYMC/phenyl-C61-butyric acid methyl ester (PCBM)/bathocuproine/Ag. We show that the derivatives introduce a dipole at the perovskite/PCBM interface, which for derivatives with suitable energy levels can enhance the charge carrier extraction, leading to a quenched photoluminescence of perovskite thin films and an improved photovoltaic performance. As a result, both a higher average and maximum power conversion efficiency could be achieved and an overall better device reproducibility. This work highlights the significant potential of energetics engineering between perovskites and transport layers in perovskite solar cells for highly efficient photovoltaic devices.