Five complex indoline alkaloids, alstolarsines A-E (1-5) possessing two unprecedented carbon skeletons of 6/5/5/7/6/6(5) fused polycyclic systems, were isolated from Alstonia scholaris. Their structures were characterized using various methods including spectroscopic data, ECD spectra, and single-crystal X-ray diffraction. The inhibitory activities of alstolarsines A-D (1-4) on DRAK2 phosphorylation and ATP-citrate lyase were evaluated, but all of them were inactive.