A star-shaped triphenylamine-benzene-1,3,5-tricarbohydrazide molecule with a twisted molecular conformation was found to display amazing multifunctional optical properties. The design of peripheral triphenylamine units and a central benzene connected with hydrazide groups leads to the formation of rare polymorphic properties in the presence of multiple flexible chains. Two polymorphs with different fluorescence colors exhibited bathochromic mechanofluorochromic activities with high contrast due to a crystalline-to-amorphous transition.