This study demonstrates a multi-responsive high-performance bilayered hydrogel actuator (HA) obtained via coating a borax cross-linked N¹,N¹-diethylethane-1,2-diamine (DEEDA)-modified polyvinyl alcohol (PVA) microgel (PVA–DEEDA–borax) on a polyacrylic acid-coated biaxially oriented polypropylene (BOPP) substrate, and reveals that the amount of borax that is added plays a decisive role in the ultimate performance of the actuator. The HA is able to perform rapid, reversible, and sustainable bidirectional self-rolling deformation actuated by heat- and moisture-triggered swelling/deswelling of PVA–DEEDA–borax gel, transforming into 2D/3D tube, wave and cross shapes through designing the assembly of actuators. The significant difference in the swelling behavior between PVA–DEEDA–borax and BOPP generates enough force to actuate the performance of the hydrogels as soft artificial muscle and self-adapted smart manipulator with capability of lifting masses much heavier than the actuator devices, showing potential applications in small-scale soft robotics.

Inverted perovskite solar cells have emerged as promising candidates for next‐generation photovoltaics due to their compatibility with tandem architectures and flexible substrates. A critical factor for high device performance is the optimization of buried interfaces using self‐assembled monolayers (SAMs), with Me‐4PACz standing out for its excellent charge extraction properties. However, a polarity mismatch between the hydrophobic carbazole terminal and the polar perovskite precursors hinders film coverage and efficient device reproducibility. Here, we report a facile post‐treatment strategy employing two chlorinated imidazole derivatives, 4,5‐dichloroimidazole (4,5‐DI) and 4,5‐dichloro‐2‐methylimidazole (4,5‐D‐2‐MI), at the Me‐4PACz/perovskite interface. These molecules enhance carbazole–imidazole interactions, convert the surface from nonpolar to polar, and improve the wettability of the SAM, resulting in an enhanced perovskite morphology. The resulting interfacial dipole modifications alter the work function and reduce the band offset at Me‐4PACz/perovskite interface, ultimately enhancing the device fill factor and photovoltage. Ultimately, the target devices delivered an efficiency of approximately 25% with improved long‐term stability under varied environmental conditions, highlighting the effectiveness of interfacial engineering via SAM post‐treatment for high‐performance and durable devices.