The thermal shape memory behavior of a series of α-amino acid-based poly(ester urea)s has been explored. We demonstrate that these materials exhibit excellent shape memory performance in dual- and triple-shape thermomechanical testing. Significant activation of chain mobility above the Tg as well as a hydrogen bonding network provide the basis for shape transformations and recovery. Additionally, we tuned the shape memory properties of these materials with polymer blending, enabling the demonstration of quadruple-shape memory cycles.