Biocatalytical upgrading of side streams from agricultural biomass into multifunctional materials constitutes a very attractive option to increase the circularity of food and material systems. We propose the design of radical scavenging hydrogels with mechanical integrity and protective effects against reactive oxygen species by enzymatic crosslinking of arabinoxylans (AX) with high ferulic acid content extracted from corn fibre using subcritical water. We have compared the influence of two enzymatic systems, laccase/O2 and peroxidase/H2O2, on the biochemical structure, multiscale assembly, physicochemical properties, and radical scavenging activity of the polysaccharide hydrogels. Peroxidase crosslinking results in instant hydrogel formation, whereas laccase shows slower crosslinking kinetics, resulting in a more elastic gel network. Characterization by size exclusion chromatography, small angle X-ray scattering, and microscopy revealed structural differences in the network organization of the hydrogels produced by the two enzymes. Laccase crosslinking leads to smaller polymeric aggregates, promoting their progressive organization in network clusters that impact the overall ultrastructure. Conversely, the fast crosslinking induced by peroxidase results in higher porosity and forms larger and potentially more heterogeneous aggregates, which seem to hinder their subsequent association in clusters. Both AX hydrogels exhibit adequate biocompatibility and protective effects against in vitro cellular oxidative stress compared to an alginate reference. This constitutes a proof of concept of the potential application of radical scavenging hydrogels from agricultural side streams for biomedical and nutritional applications in wound healing, cellular repair and targeted delivery.