Formation of sporopollenin, the major outer cell wall component of pollen and spores, is one of the critical innovations for plant landing and dispersal in the terrestrial environment, whereas biosynthesis and composition of sporopollenin are not yet fully revealed. In this study, we show that sporopollenin of seed plants contain both hydroxycinnamates and lignin guaiacyl units. Genetic analysis showed that mutations of phenylpropanoid pathway resulted in defective sporopollenin. Further studies showed that the phenylpropanoid derivatives in sporopollenin play an important role in protection against threatening of the UV radiation. Finally, we provide evidence that different kinds of phenylpropanoid derivatives in sporopollenin in bryophyte, pteridophyte and seed plant are correlated with evolution after plant landing. Together, our results indicate that phenylpropanoid derivatives are essential component of sporopollenin functioning in protection of microspores/pollen from UV radiation under the terrestrial environment.