[structure: see text] A pair of geometrically isomeric monoterpenoid indole alkaloids with a skeleton rearrangement and two additional carbons, named (19,20) E-alstoscholarine (1) and (19,20) Z-alstoscholarine (2), were obtained from the leaf extract of Alstonia scholaris. Their structures were elucidated on the basis of spectroscopic methods and then confirmed by X-ray crystal diffraction. The biogenesis of these compounds was also proposed.