The synthesis of high loading and recyclable pentaerythritol supported imidazolidin-4-one catalyst I and its application in enantioselective Diels–Alder reactions of cyclopentadiene and α,β-unsaturated aldehydes with high performance were described. Especially noteworthy, the pentaerythritol supported imidazolidin-4-one with high loading capacity can be recovered by simple precipitation and filtration, and recycled for up to four runs without observing significant decrease in catalytic activity.