The aza-Diels–Alderreaction between benzaldimines 1 and Danishefsky's diene in solvent-free conditions is reported for the first time. The reaction occurs rapidly at 30 °C and is catalyzed by porous α-zirconiumhydrogenphosphate (p-αZrP) in the presence of sodiumdodecylsulfate (SDS). The yields were excellent. The recycling of the catalyst has also been investigated.