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.