Nano-wrinkled polymeric membranes have received tremendous attention for their broad applications in tunable optics, biomedicine, surface wettability, and flexible electronics. However, achieveing a low-cost and scalable synthesis routine remains highly desirable. Here, we invent a simple, bottom-up, polymer engineering strategy by introducing water molecules into the polymerization process. Water evaporation induces intermolecular forces that build a crosslinking reaction gradient from the material surface to its interior, which buckles the surface-forming wrinkles. The shape, geometry, size, orientation, and arrangement of the wrinkles on the polymer surface can be designed accordingly. Moreover, the as-fabricated nano-wrinkled, polymeric membranes display outstanding performance in energy and sensing applications, boosting output current and sensing sensitivity by 611% and 164%, respectively, compared to their flat counterparts. This work may contribute to a low-cost, scalable, and environmentally friendly strategy to engineer polymer surfaces with controllable wrinkles, showing great potential for the development of various soft-matter technologies.

纳米褶皱聚合物膜因其在可调光学、生物医学、表面润湿性和柔性电子领域的广泛应用而受到极大关注。然而，实现低成本和可扩展的合成程序仍然是非常可取的。在这里，我们通过将水分子引入聚合过程，发明了一种简单的、自下而上的聚合物工程策略。水分蒸发会引起分子间作用力，从而在材料表面到其内部形成交联反应梯度，从而使形成表面的皱纹弯曲。聚合物表面皱纹的形状、几何形状、大小、取向和排列可以相应地设计。此外，制造的纳米褶皱聚合物膜在能源和传感应用中表现出出色的性能，与平坦的同类产品相比，输出电流和传感灵敏度分别提高了 611% 和 164%。这项工作可能有助于低成本、可扩展和环保的策略来设计具有可控皱纹的聚合物表面，显示出开发各种软物质技术的巨大潜力。