Psychotropic fungi of the genus Psilocybe, colloquially referred to as "magic mushrooms", are best known for their l-tryptophan-derived major natural product, psilocybin. Yet, recent research has revealed a more diverse secondary metabolism that originates from this amino acid. In this minireview, the focus is laid on l-tryptophan and the various Psilocybe natural products and their metabolic routes are highlighted. Psilocybin and its congeners, the heterogeneous blue-colored psilocyl oligomers, alongside β-carbolines and N,N-dimethyl-l-tryptophan, are presented as well as current knowledge on their biosynthesis is provided. The multidisciplinary character of natural product research is demonstrated, and pharmacological, medicinal, ecological, biochemical, and evolutionary aspects are included.