<p>Nonionic poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA)-based inverted wide-bandgap perovskite solar cells (PSCs) are pivotal for advancing all-perovskite tandem architectures and indoor photovoltaics, yet their performance is fundamentally constrained by the hydrophobic nature of PTAA. Herein, we demonstrate a dual-interface molecular engineering strategy to synchronously modulate the perovskite-facing upper interface and substrate-contacting buried interface of PTAA using hydrophilic poly(methyl methacrylate) (PMMA) and poly(3-carboxypentyl thiophene) (P3CT-N). The carbonyl (C=O) groups in PMMA and P3CT-N synergistically enhance interfacial wettability, promoting the controlled crystallization of 1.78 eV wide-bandgap perovskites. Additionally, the carbonyl coordination effectively passivates undercoordinated Pb²⁺ defects, improving charge transport dynamics. Meanwhile, vacuum-level shifting induced by the interface dipole of PMMA and P3CT-N optimizes valence-band alignment, facilitating efficient hole extraction. As a result, the modified PTAA-based single-junction PSCs achieve a remarkable power conversion efficiency (PCE) of 19.38% under AM 1.5G illumination, significantly surpassing the 17.06% of pristine PTAA devices. The sandwich polymer structure-based PTAA design further enhances indoor photovoltaic performance, yielding PCEs of 37.43% and 30.09% under 1000 lux and 200 lux LED illumination, respectively. Moreover, in all-perovskite tandem configurations, the modified hole transport layer (HTL) enables a remarkable PCE of 26.87% under AM 1.5G illumination, outperforming control devices (25.38%). This strategy provides a robust pathway toward highly efficient and stable indoor and all-perovskite tandem photovoltaics based on wide-bandgap perovskite.</p>