Secondary metabolites are essential when considering the ecological context in which an organism operates. They have an array of functions, related to signalling and dealing with biotic and abiotic stress situations. For defence against pathogenic fungi, plants can synthesize various metabolites. Wheat, like several other cereals, produces various benzoxazinoids, which are also associated with herbicide detoxification and the defence against herbivores and microorganisms. Apart from these benzoxazinoids, wheat seems to produce only a limited number of other metabolites with known antifungal activity when compared to other cereals. Nevertheless, wheat is still capable of successfully defending itself against pathogenic fungi by outsourcing its defences, that is, through the mobilization of the microbial community. This chapter provides an overview of the way in which these natural antimicrobial compounds contribute to the defence of wheat against fungal pathogens, as well as considering the counter defensive actions undertaken by some of those fungal pathogens.