Remarkable progress on the biology of plant secondary metabolism has recently been realized. The application of advanced biochemistry, molecular, cellular, and genomic methodologies has revealed biological paradigms unique to the biosynthesis of secondary metabolites, including alkaloids, flavonoids, glucosinolates, phenylpropanoids, and terpenoids. The use of model plant systems has facilitated integrative research on the biosynthesis and regulation of each group of natural products. The model legume, Medicago truncatula Gaertn., plays a key role in studies on phenylpropanoid and flavonoid metabolism. Mint ( Mentha × piperita L.) and various conifers are the systems of choice to investigate terpenoid metabolism, whereas members of the mustard family (Brassica spp.) are central to work on glucosinolate pathways. Arabidopsis thaliana (L.) Heynh. is also used to study the biosynthesis of most secondary compounds, except alkaloids. Unlike other categories of secondary metabolites, the many structural types of alkaloids are biosynthetically unrelated. The biology of each group is unique, although common paradigms are also apparent. Opium poppy ( Papaver somniferum L.) produces a large number of benzylisoquinoline alkaloids and has begun to challenge Madigascar periwinkle ( Catharanthus roseus (L.) G. Don), which accumulates monoterpenoid indole alkaloids, as the most versatile model system to study alkaloid metabolism. An overview of recent progress on the biology of plant alkaloid biosynthesis, with a focus on benzylisoquinoline alkaloid pathways in opium poppy and related species, highlights the emergence of opium poppy as an important model system to investigate secondary metabolism.