In this paper, for the first time, photopolymers were synthesized from glycerol acrylates with different numbers of functional groups, 2-hydroxy-3-phenoxypropyl acrylate, glycerol dimethacrylate or glycerol trimethacrylate, without and with the addition of vanillin styrene. The photocuring kinetics were monitored by real-time photorheometry. The mechanical, rheological, thermal, antimicrobial and shape-memory properties of the photopolymers were investigated. All polymers synthesized demonstrated antibacterial activity against Escherichia coli and Staphylococcus aureus, as well as antifungal activity against Aspergillus flavus and Aspergillus niger. 2-Hydroxy-3-phenoxypropyl acrylate-based polymers showed thermoresponsive shape-memory behavior. They were able to maintain their temporary shape below the glass transition temperature and return to their permanent shape above the glass transition temperature. Synthesized photopolymers have potential to be used as sustainable polymers in a wide range of applications such as biomedicine, photonics, electronics, robotics, etc.