Stereoselective synthesis of exocyclic enones 10-17 via a base-catalyzed direct aldol condensation between dihydrolevoglucosenone 1 and heterocyclic aldehydes 2-9 is described. The reaction is performed under mild conditions and is applicable to variety of heterocyclic aldehydes. E-Steroisomers of exo-cyclic enones are the only products. They are very easy to isolate and were formed in good to excellent (72-88%) yield. 1H NMR, 13C NMR analyses provide the structural assignment and absolute stereochemistry of the condensation products. Single-crystal X-ray diffraction of condensation product 12, additionally supports the structural assignment.