Abstract: Coiled rodlets characterize several non‐related taxa within the angiosperms. They often occur together with tubules but sometimes also with platelets or transitional forms between them. The ultrastructure chemistry, and recrystallization of epicuticular waxes of three species were investigated by high‐resolution scanning electron microscopy, gas chromatography, and mass spectrometry. Whereas Buxus sempervirens (Buxaceae) and Chrysanthemum segetum (Asteraceae) show coiled rodlets in combination with tubules, Leymus arenarius (Poaceae) exhibits tubules but no coiled rodlets. Chemical analyses reveal that the predominating β‐diketones of all species differ completely in their molecular structure. Those of the former two species are mainly substituted in carbon atom positions up to 12. In contrast, the wax of L. arenarius contains only hentriacontane‐14,16‐dione and 25‐hydroxy‐hentriacontane‐14,16‐dione. Standard solutions of the total waxes from B. sempervirens, C. segetum and L. arenarius, the purified β‐diketone fraction from C. segetum and hentriacontane‐14,16‐dione from Secale cereale were taken for recrystallization experiments under different conditions in relation to solvent and crystallization velocity. It was demonstrated that coiled rodlets grew exclusively from total waxes of B. sempervirens and C. segetum, and its β‐diketone fraction but never from L. arenarius wax or pure hentriacontane‐14,16‐dione. The recrystallization experiments pointed out that conditions, such as the chemical environment and physical factors, strongly influence the formation of coiled rodlets and tubules. It is concluded that coiled rodlets are formed by self‐assembly in close dependence on the position of β‐diketo substitution. The future role of β‐diketones in the classification of coiled rodlets within wax crystals is discussed.