Carbon- and silica-based nanomaterials possess a set of merits including large surface area, good structural stability, diversified morphology, adjustable structure, and biocompatibility. These outstanding features make them widely applied in different fields. However, limited by the surface free energy effect, the current studies mainly focus on the symmetric structures, such as nano-spheres, nanoflowers, nanowires, nanosheets, and core–shell structured compos-ites. By comparison, the asymmetric structure with ingenious adjustability not only exhibits a larger effective surface area accompanied with more active sites, but also enables each component to work independently or corporately to har-ness their own merits, thus showing the unusual performances in some specific applications. The current review mainly focuses on the recent progress of design principles and synthesis methods of asymmetric carbon- and silica-based nano-materials, and their applications in energy storage, catalysis, and biomedicine. Particularly, we provide some deep insights into their unique advantages in related fields from the perspective of materials\' structure–performance relationship. Fur-thermore, the challenges and development prospects on the synthesis and applications of asymmetric carbon- and silica-based nanomaterials are also presented and highlighted.