Four new minor alkaloids, stryvomicine A (1), deoxy-isostrychnine-chloromethochloride (2), β-colubrine-chloromethochloride (3) and α-colubrine-chloromethochloride (4) were isolated from the seeds of Strychnos nux-vomica. Stryvomicin A possesses an unprecedented 6/5/7/8/6/7/6 heptacyclic ring system, which is the first example of the linkage of the C3–O–C26–N4 bond in strychnan-type alkaloids. Compound 5 induced the occurrence of autophagy and might have potential implications in autophagy related diseases.