Three new photoactive polymeric materials embedding a hexanuclear molybdenum cluster (Bu4N)2[Mo6I8(CH3COO)6] (1) have been synthesized and characterized by means of Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and emission spectroscopy. The materials are obtained in the format of transparent and thin sheets, and the formulations used to synthesize them are comprised of 2-hydroxyethyl methacrylate (HEMA), as a polymerizable monomer, and ethylene glycol dimethacrylate (EGDMA) or poly(ethylene glycol)dimethacrylate (PEGDMA), as cross-linkers. All the polymeric hydrogels generate singlet oxygen (1O2) upon irradiation with visible light (400-700 nm), as demonstrated by the reactivity toward two chemical traps of this reactive species (9,10-dimethylanthracene and 1,5-dihydroxynaphthalene). Some differences have been detected between the photoactive materials, probably attributable to variations in the permeability to solvent and oxygen. Notably, one of the materials resisted up to 10 cycles of photocatalytic oxygenation reactions of 1,5-dihydroxynaphthalene. All three of the polyHEMA hydrogels doped with 1 are efficient against S. aureus biofilms when irradiated with blue light (460 nm). The material made with the composition of 90% HEMA and 10% PEGDMA (Mo6@polymer-III) is especially easy to handle, because of its flexibility, and it achieves a notable level of bacterial population reduction (3.0 log10 CFU/cm2). The embedding of 1 in cross-linked polyHEMA sheets affords a protective environment to the photosensitizer against aqueous degradation while preserving the photochemical and photobactericidal activity.