Recently, special attention has been paid to the syntheses of micro/nanostructured crystallites with high‐energy crystal facets, because high‐energy crystal surfaces usually exhibit fascinating surface‐enhanced properties and have promising applications in catalysis, photoelectrical devices, and energy conversion, etc. With particular emphasis on the results obtained by the authors’ research group, this feature article gives a brief review of recent progress in the field of surface/morphology controlled syntheses, focusing on high‐energy crystal surfaces of five kinds of inorganic functional material, with the wurtzite, rocksalt, anatase, rutile, and face‐centered cubic structures, respectively. Combined with the theoretical and experimental research results as well as crystal structure models, the intrinsic causes for surface‐dependent chemical/physical properties of those materials with high‐energy surfaces are further discussed.