The inverted p-i-n perovskite solar cells hold high promise for scale-up toward commercialization. However, the interfaces between the perovskite and the charge transport layers contribute to major power conversion efficiency (PCE) loss and instability. Here, we use a single material of 2-thiopheneethylammonium chloride (TEACl) to molecularly engineer both the interface between the perovskite and fullerene-C60 electron transport layer and the buried interface between the perovskite and NiOx-based hole transport layer. The dual interface modification results in optimized band alignment, suppressed nonradiative recombination, and improved interfacial contact. A PCE of 24.3% is demonstrated, with open-circuit voltage (Voc) and fill factor (FF) of 1.17 V and 84.6%, respectively. The unencapsulated device retains >97.0% of the initial performance after 1000 h of maximum power point tracking under illumination. Moreover, a PCE of 22.6% and a remarkable FF of 82.4% are obtained for a mini-module with an active area of 3.63 cm2.