To broaden the types and scope of use of shape-memory polymers (SMPs), we added the hindered phenol 3,9-bis[1,1-dimethyl-2-{b-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro-[5,5]-undecane (AO-80), which comprises small organicmolecules, to acrylic rubber (ACM) to form a series of AO-80/ACMrubber composites. The structural, thermal, mechanical property, and shape-memory properties of the AO-80/ACMrubber composites were investigated. We identified the formation of intra-molecular hydrogen bonding between -OH of AO-80 and the carbonyl groups and the ether groups of ACM molecules. The amount of AO-80 used can be adjusted to tailor the transition temperature. AO-80/ACM rubber composites showed excellent shape recovery and fixity. The approach for adjusting the transition temperature of AO-80/ACM rubber composites provides remarkable ideas for the design and preparation of new SMPs.