UV‐curing 3D printing technology is one of the technologies with the highest molding efficiency and accuracy in the field of 3D printing. At present, the main problems of UV‐curing 3D printing materials include the high curing shrinkage and the low toughness. In this work, free radical/cation hybrid curing system was developed, the effects of expansion monomer (DHOM, 3,9‐diethyl‐3′,9′‐dihydro‐xymethyl‐1,5,7,11‐tetraoxaspiro[5,5]undecanone) on the curing shrinkage, toughness, and other properties of the epoxy acrylate‐based UV‐curing 3D printing materials were investigated. The results showed that when the added amount of DHOM was 15 wt%, the best comprehensive performance of UV‐curing 3D printing materials was obtained. At this time, the curing shrinkage rate decreased from 6.13% to 3.47%. The main reason was that DHOM undergoes ring‐opening polymerization under the action of cationic photoinitiator, resulted in volume expansion. The impact strength increased from 9.61 to 12.13 KJ/m2, which was because that the ring‐opening reaction of DHOM reduced the curing shrinkage of the resin system and released the internal stress between the resin molecules.