Rice (Oryza sativa) is a staple food crop and serves as a model cereal crop plant for scientific study. Phytochemical investigations of the agronomically devastating rice blast disease have identified a number of rice phytoalexins exhibiting significant direct anti-fungal activity against the causative agent, Magneporthe grisea. Current evidence strongly indicates that these phytoalexins, largely a family of labdane-related diterpenoids, are important as general antibiotics, and that similar phytoalexins are produced more broadly throughout the cereal crop family. From the extensive sequence information available for rice it has been possible to functionally identify the genes for the enzymes catalyzing the two consecutive cyclization reactions that initiate biosynthesis of these labdane-related diterpenoid phytoalexins. This has led to several insights into the underlying evolution of diterpene biosynthesis throughout the cereal crop family. The hydrocarbon olefins resulting from cyclization must be further elaborated to form bioactive natural products and, because not much is currently known, necessarily speculative biosynthetic pathways for these processes are presented. Given the significant antibiotic activity of the labdane-related diterpenoid phytoalexins from rice, and the presence of similar secondary metabolism throughout the cereal crop plant family, study of this type of biosynthesis will continue to be an area of active investigation.