and, in particular, micro/nanostructure on their surfaces plays an important role in numerous natural systems. [7][8][9][10] For example, carp, filefish, and seaweed can keep themselves clean in oil-polluted water because of the existence of micro/ nanohierarchical structured hydrogel material on their surface. [11,12] The wharf roach (Ligia exotica) and pitcher plant harness their surface microscaled morphologies to control liquid transportation for survival. [13,14] Inspired by the nature biological material, constructing structured functional surface of hydrogel-based materials has become one of the most promising solutions for the researchers to satisfy the increasing need of novel functional materials. Current fabrication strategies mainly focus on surface chemical modifications, [15][16][17] template replica, [18][19][20][21] photolithography, [22] laser scanning, [23] and 3D printing. [24] However, these methods suffer from complicated manufacturing process and specific material modeling, which have been demonstrated to restrict the large-area fabrication and thus limit their practical applications. With the increasing interest in properties associated with complex structured surfaces, a simple and scalable method is intriguing and urgent to be developed in order to fabricate various desired structured hydrogel surfaces. [25][26][27] Here, we report a general strategy for constructing microand nanostructured hydrogel surfaces in the miscible polymer diffusion layer directly during the process of gel formation. This strategy relies on the interplay between polymer chain diffusion and the subsequent freezing-induced gelation and microphase separation processes. The proposed method exploits the interface of two miscible polymers, one of which needs to undergo gelation. Our strategy is accomplished through two successive processes, i.e., the diffusion-driven mixing process followed by the freezing-induced gelation and microphase separation. The former forms a diffusion layer, while the latter produces structures in this diffusion layer. The gelation couples to the microphase separation and they finally determine the micro/ nanostructures on the gel surfaces. Meanwhile, the hydrogel surfaces with the gradient structure and patterned surfaces can also be regulated through the control of gelation temperature and diffusion areas. Moreover, the micro/nanocomposite Hydrogels with multiscale structured surface have attracted significant attention for their valuable applications in diverse areas. However, current strategies for the design and fabrication of structured hydrogel surfaces, which suffer from complicated manufacturing processes and specific material modeling, are not efficient to produce structured hydrogel surfaces in large area, and therefore restrict their practical applications. To address this problem, a general and reliable method is reported, which relies on the interplay between polymer chain diffusion and the subsequent freezing-induced gelation and microphase separation processes. The basic idea ...