Pleiokomenines A and B (1 and 2), first examples of dimeric aspidofractinine alkaloids linked by a methylene bridge, were isolated from the stem bark of Pleiocarpa mutica. Their structures were elucidated by a combination of spectroscopic analyses and semisynthetic derivatization of pleiocarpinine (3) and a formaldehyde equivalent mediated by scandium trifluoromethanesulfonate. Pleiokomenines A (1) and B (2) showed moderate antiplasmodial activities in the micromolar range against the FcB1 strain. © 2017 American Chemical Society.