Hybrid perovskites stand out as one of the leading materials in the new generation of photovoltaics. Their stability under operating conditions, however, remains an ongoing challenge. In particular, aging at the interface with the charge transport materials contributes to the degradation during operation. To address this, functionalized triarylamine-based modulators are employed, which are known to form hole-transporting supramolecular stacks, at the interface between the perovskite active layer and the hole-transporting material in conventional perovskite solar cells. As a result, the improvements of the operational stabilities are demonstrated without compromising device performances, providing a promising strategy for advancing photovoltaics.|Triarylamine modulators at the interface between the perovskite active layer and the hole-transporting material in perovskite solar cells act as charge-mediating transfer layers, demonstrating improvements of the operational stabilities without compromising performances, which reveals a promising strategy for advancing perovskite photovoltaics. image