Polymers of urethane diacrylate containing an aliphatic or aromatic backbone chain were prepared in the presence of a number of monofunctional and polyfunctional monomers under UV curing. These monomers have different glass transition temperatures ranging from — 110° to 250°C. Film hardness, gel content, tensile properties, and shape recovery characters of these polymers were determined. A correlation between the glass transition temperatures and these properties was established. The monomerN-vinyl pyrrolidone demonstrated the best performance in the preparation of polymers. Some of these polymer films have achieved a unique character of shape recovery phenomenon.