The development of a stereoselective aza‐Piancatelli reaction to access 4‐aminocyclopentenones is reported. This transformation relies on the use of chiral o‐sulfinyl anilines as chiral inductors to afford the targeted products in good to excellent yields. Remarkably, the high value‐added cyclopentenones could be obtained in drs up to >95:5, depending upon the furan substitution pattern. [ABSTRACT FROM AUTHOR]