Thiopyrano[4,3,2‐cd]benzofuran 9 possessing benzofuran and methylenethiopyran structures in the molecule was synthesized starting from 1‐chloro‐4‐methoxy‐2‐nitrobenzene 11. Some reactions (formylation, protonation and catalytic hydrogenation) on 9 were examined. The 2‐position of 9 was highly reactive toward electrophilic reagents and the furan ring was readily reduced by catalytic hydrogenation with palladium‐charcoal. Thiopyrano[4,3,2‐cd]benzofuran 9 has both properties of methylenethiopyran and benzofuran. Copyright © 1992 Journal of Heterocyclic Chemistry