The absolute stereochemistry of ophiorrhizine, a C₁₉ pentacyclic quaternary indole alkaloid from Ophiorrhiza major RIDL. with known structure and relative stereochemistry, was inferred to be (-)-1 but required verification. We report the first chiral synthesis of (-)-ophiorrhizine using the "cincholoipon-incorporating lactim ether route". Lactim ether (+)-4, derived from cincholoipon ethyl ester [(+)-3], was coupled with 6-benzyloxy-3-chloroacetylindole (6) to form lactam ketone (+)-8, followed by sequential reactions through intermediates (+)-9, (+)-10, 11, (-)-12, (-)-13, 14, (-)-15, and (-)-16 to yield (-)-1·H₂O. Synthetic (-)-1·H₂O showed identical UV (MeOH), IR (KBr), ¹H-NMR (CD₃OD), ¹³C-NMR (CD₃OD), and CD (MeOH) spectra, TLC mobility, and specific rotation to natural ophiorrhizine, unequivocally establishing its absolute stereochemistry as (-)-1. This synthesis chemically correlates ophiorrhizine with the Cinchona alkaloid cinchonine [(+)-2] (since (+)-4 is prepared from (+)-2 via cincholoipon ethyl ester [(+)-3]) and enhances the usefulness of our route for chiral syntheses of Corynanthe-type indoloquinolizidine alkaloids.