Europium-β-diketone chelate doped poly(methyl methacrylate) and poly(methyl methacrylate)/poly(ethylene co-vinyl acetate) blends have been successfully prepared and characterized. The mechanical properties of the PMMA-EVA systems have been assessed in terms of tensile strength and impact strength. The thermal characteristics and the energy involved in thermal decomposition have been studied. The structural properties of the complex doped polymeric systems reveal that the complex exists in the same crystalline state in the doped systems as it does in the pure state. The orientations of the groups in the host matrix have been found to be affected by the complex loading. The optical properties of the system have been studied by photo luminescence spectroscopy. The fluorescence lifetime have been observed to decrease at greater loadings of the complex; an effect that has been attributed to concentration quenching. The complex doped PMMA/EVA polymer network developed is considered to be a potential candidate for the development of optoelectronic devices those possess superior mechanical properties.