Two novel dimeric indole alkaloids were isolated from the leaves and twigs of Psychotria henryi. Their structures were established by chemical and spectroscopic methods. Compound 1 was a novel dimeric tryptamine-related alkaloid that contained an unprecedented decacyclic ring system, and compound 2 featured a pyrido[3,4-b]indole moiety adjacent to a pyrrolidinoindole skeleton. The absolute configurations of compounds 1 and 2 were determined by calculation of electronic circular dichroism (ECD) using density functional theory (DFT). CI - Copyright (c) 2013 Elsevier B.V. All rights reserved.