This study investigated the effect of bioactive micro-fillers on the light transmittance and polymerization of three commercially available bulk-fill resin composites. These were mixed with 20 wt% bioactive glass 45S5, Portland cement, inert dental barium glass, or nothing (controls). Composites were photo-activated and light transmittance through 4 mm thick specimens was measured in real time. Moreover, degree of conversion (DC) and Knoop hardness (KHN) were assessed. Light transmittance of all bulk-fill composites significantly decreased (p < 0.05) with addition of 20 wt% bioactive glass 45S5 but not when inert barium glass was added. For bulk-fill composites modified with Portland cement, light irradiance dropped below the detection limit at 4 mm depth. The DC at the top surface of the specimens was not affected by addition of bioactive or inert micro-fillers. The bottom-to-top ratio of both DC and KHN surpassed 80% for bulk-fill composites modified with 20 wt% bioactive or inert glass fillers but fell below 20% when the composites were modified with Portland cement. In contrast to Portland cement, the addition of 20 wt% bioactive glass maintains adequate polymerization of bulk-fill composites placed at 4 mm thickness, despite a decrease in light transmittance compared to the unmodified materials.