Hierarchical ceramic structures offer great potential for multitudinous industrial applications (e.g., cell alignment) due to their intrinsic hydrophilic and environmental resistance properties. However, to date, the fabrication of hierarchical ceramic structures requires specific equipment (e.g., high vacuum systems) and time-consuming processes; such requirements limit the practical utilization of hierarchical ceramics. In this study, we combined ceramic thin films produced from interfacial sol–gel reactions and surface wrinkling from elastomer cross-linking contraction; we conducted a dynamic interfacial release process to fabricate hierarchically wrinkled mesoporous ceramic surfaces on soft elastomers. The parameters of sol–gel reactions, including precursors, acid/base-catalysts, aging time, and temperature, were systematically controlled to demonstrate the feasibility of sol–gel reactions for fabrication of hierarchically mesoporous ceramic wrinkled surfaces (i.e., mesopores on a microsized wrinkled surface). Furthermore, the wrinkled surfaces demonstrated great enhancement of growth alignment of human blood vessel cells. Thus, we developed a simple (yet cost-effective), mold-free, large-area, and hierarchical ceramic wrinkle formation process; it can be used in many practical applications, such as cell culture, microfluidic chips, antiskidding surfaces, antiglare structures, and photoelectric devices.