Shape memory polymers are promising materials for smart biomedical devices and applications, however, thermal systems are limited by a narrow applicable temperature range. Light-induced shape memory (LSM) circumvents this limitation by using a mechanism independent of heat that can be remotely triggered. This work presents the synthesis and characterization of multiple photo-responsive polyester platforms which contain regularly repeating pendant cinnamic acid derivatives. Elastomeric thermoset poly(ester urethane)s (P-PEUs) synthesized by step-growth polymerization of novel bifunctional monomers possessed a range of thermal and mechanical properties that likened them to a variety of soft tissues found in the body, as well as boasted negligible cytotoxicity and physiological degradation. All P-PEUs displayed LSM, with those in the DCA series also exhibiting thermal shape memory which afforded two independent triggers which when combined allowed for the programming and recovery of a novel multifunctional triple shape material, capable of switching on macroscopic and microscopic scales. Photo-responsive poly(β-amino ester)s (PBAEs) were synthesized by functional monomer or post-polymerization route to give soft elastomeric materials containing photo-groups as well as additional reactive functionality to be used for further modification of chemical and physical properties. All materials were characterized by 1H-NMR, GPC, TGA, DSC, DMA, and Instron.