Abstract The synthesis of the novel enamide isoquinoline alkaloid polycarpine, (Z)‐1‐(2′‐hydroxy‐3′,4′‐dimethoxy‐benzylidene)‐3,4‐dihydro‐6,7‐dimethoxy‐2‐(1H)isoquinolinecarboxaldehyde, proceeding from commercially available 2′,3′,4′‐trimethoxyacetophenone in seven steps is described. TheO‐methyl andO‐benzyl derivatives were also obtained.