<jats:title>Abstract</jats:title><jats:p>Psychotriasine was isolated from the leaves of <jats:italic>Psychotria calocarpa</jats:italic> (Rubiaceae). The structure was established by spectroscopic methods including 2D‐NMR analysis. To the best of our knowledge, psychotriasine is the first example of a dimeric tryptamine‐related alkaloid that contains a free <jats:italic>N</jats:italic><jats:sup><jats:italic>α</jats:italic></jats:sup>‐methyltryptamine unit in the molecule.