<jats:title>Abstract</jats:title><jats:p>Two new indole alkaloids, angustilodine (<jats:bold>1</jats:bold>), with an unprecedented pentacyclic carbon skeleton, and angustilocine (<jats:bold>2</jats:bold>), belonging to the <jats:italic>seco</jats:italic>‐angustilobine‐B group of alkaloids, were obtained from the leaf extract of the Malayan species <jats:italic>Alstonia angustiloba</jats:italic>, and their structures were established by spectroscopic analysis.