The complete 1 H and 13 C NMR assignments of a trimeric vindoline together with its individual components, dimeric vindolicine and monomeric vindoline, are performed based on a thorough analysis of the ROESY, COSY, HSQC, and HMBC spectra in combination with the state-of-the-art quantum-chemical calculations. A spatial structure of vindoline trimer is determined by means of computational conformational analysis in combination with the probability distribution map of its basic conformers. On the example of monoterpene indole alkaloid, the trimer vindoline, the present study reveals the power of modern computational NMR to perform identification and stereochemical studies of large natural compounds with some limitations, that may arise in the quantum chemical computing workflow.