The first catalytic asymmetric total synthesis of (+)- and (−)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels–Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels–Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (−)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.