Advancements in polymer chemistry have enabled the design of macromolecular structures with tailored properties for diverse applications. Reversible addition-fragmentation chain-transfer (RAFT) polymerization is a controlled technique for precise polymer design. Automation tools further enhance polymer synthesis by enabling the rapid, reproducible preparation of polymer libraries. This study utilizes an automated platform and a biologically friendly bio-Fenton RAFT synthesis method to create hydrogels with embedded star polymers derived from complex block copolymers with controlled block lengths and sequences. Automation improves the efficiency compared to manual methods, while the choice of prepolymer and polymerization techniques ensures biocompatibility. Hydrogels formed by cross-linking linear block copolymers exhibit tunable physical, chemical, and mechanical properties. By systematically altering the prepolymer block sequences, promising hydrogel candidates for enhanced cell biocompatibility and proliferation are identified. These synthetic hydrogels mimic cellular microenvironments and offer a robust platform for biomedical applications, paving the way for an efficient hydrogel design and synthesis.