Secondary metabolites are compounds that are not required for sustenance of organisms but play an important role in protecting them against biotic and abiotic stresses. Extensive literature available on the subject covers their role in sexual reproduction of seed plants only to a limited extent. Secondary metabolites play a critical role in pollination in pollinator-dependent plants by attracting pollinators. In gymnosperms, insect pollinators are involved, along with wind in members of Cycadales and Gnetales, in which both male and female cones emit volatile compounds as attractants. Nearly 90% of angiosperms are pollinated by a range of animals. Apart from acting as visual and olfactory attractants for pollinators, floral volatiles also act as rewards to specific pollinating insects in some species. Secondary metabolites present in the nectar and stigma act as antimicrobial and insecticidal agents and thus protect them against general infection and theft; they also repel nonpollinating visitors from flowers. In species that achieve pollination through sexual deception without offering any rewards, flowers emit secondary metabolites in the form of species-specific pheromones to attract male pollinators. Floral volatiles also play an important role in pollinator-driven speciation, particularly in species showing highly specialized pollination systems; any change in a specific volatile compound due to a mutation may bring about reproductive isolation of the mutant by attracting a new pollinator instead of the regular pollinator of the species. Thus, floral volatiles have played a key role in the evolutionary success of angiosperms by making pollination more efficient and facilitating reproductive isolation. In the light of the prevailing pollinator crisis due to global warming, there is enormous scope for studies on floral volatiles through application of recombinant DNA and gene-editing technologies.