Syntheses routes to obtain HA-AE and HA-NB of the same degree of functionalization and in one step under aqueous conditions were developed, and the protocols were optimized to minimize the time and solvent required for dialysis. In photorheology and DLP printing studies, HA-NB crosslinked over 4 times faster than HA-MA. Both thiol-ene inks showed higher temporal control over the network formation, with stiffness only increasing during illumination while the stiffness of the HA-MA network continued to rise in the dark state between illumination periods. Because of the different network structures, the stiffness of the thiol-ene hydrogels was lower than in the methacrylated ones after extended photopolymerization. Scaffolds with feature sizes down to 100 µm were obtained with the HA-NB variant. Our results quantify the advantages of thiol-ene vs.