A facile method is reported to manipulate a diphenylalanine peptide into hierarchically ordered structures with interesting peony-like flower morphology in the organic solvent tetrahydrofuran. The flowers formed in THF and showed, by scanning electron microscopy, that they are actually flake-built spherical aggregations, while the aggregations of FF that formed in other chosen organic solvents, such as DMSO and pyridine, show dispersive flakes. The building of the flower-like architectures is correlated to a nonclassical crystallization pathway. The similarity between the as-obtained peptide mesocrystals formed in different solvents has been investigated and discussed. Due to the roughness of the hierarchical peptide assemblies, an antiwetting surface is readily constructed with a low surface free energy fluoroalkylsilane.