The need of innovative, multifunctional biomaterials for the partial or complete tissue replacement is the driving-force for the search of improvements of the performances of the available materials and in the formulation of new ones. Addressing the focus to vitreous substitution, we have explored the possibility of using injectable aqueous solutions of poly(vinyl alcohol), PVA, derivatives able to form hydrogels in the ocular cavity upon UV-vis irradiation with visible light. In particular, we describe the features of hydrogels from methacrylate grafted PVA, PVA-MA, in terms of structural characteristics, degradation processes, release of low- and high- molecular weight molecules, and in vitro gelation kinetics. The mechanical properties, drug delivery tests, and theology tests suggest that PVA-MA derivatives have the potential to become a useful material for vitreous substitution.