In physiological fluid, a layer of hydroxycarbonate apatite, similar to bone mineral, develops on the surface of Bioglass 45S5. Collagen from the surrounding tissue is adsorbed on this layer that attracts osteoblasts, and favors bone regrowth. Bioglass is therefore an osteoinductive material. Still, due to its brittleness, the glass alone cannot be used to heal large bone defects. To overcome this issue, Bioglass is used to form a composite scaffold with poly(D,L-lactide) (PDLLA), a biodegradable polymer. The goal of this work is to understand Bioglass reactivity throughout scaffold fabrication via a low-temperature route, the solvent casting and particulate leaching technique. Changes in Bioglass (especially its surface) are susceptible to occur both while in contact with the processing fluids and potentially through a reaction with the surrounding polymeric matrix. Here we analyzed the surface changes of three different Bioglass samples: (i) as-received, (ii) treated in solutions that parallel those used in scaffold fabrication, and (iii) extracted from the scaffolds. We showed that extracted, just like treated, Bioglass deviates from the as-received, but to a larger extent. X-ray photoelectron and infrared spectroscopy support the theory that Bioglass surface was modified not just through contact with the solutions in scaffold fabrication, but upon an interaction with the polymeric matrix. The polymer network slows down the Na+/H+ exchange between Bioglass and water used to leach salt particles to create pores within the scaffold. Changes in surface properties affect the bioactivity of Bioglass and thus of the composite scaffolds, and are therefore critical to identify.