Recently, porous polymer-ceramic composites have been developed and represent promising scaffolds to be used as synthetic extracellular matrix in bone tissue engineering since they combine the advantages of these two types of materials. On the other hand bioactive glasses (BG) have been used as ceramic fillers to promote bioactivity and to enhance mechanical properties and osteoblast functions. Among all the requirements, these 3D porous structures should have a controllable average pore size larger than 100 μm as well as good pore interconnectivity to allow vascularization and tissue ingrowth. The goal of this study is to investigate the effect of the addition of a bioactive glass on the porous structure development of the scaffolds prepared by thermally induced phase-separation and also to test the bioactivity of these composite scaffolds. Poly (L-lactic) acid (PLLA) was chosen as the polymer matrix because of its well-known biocompatibility and adjustable physical and mechanical properties. Micron-sized (<10 μm) glass from the 3CaO.P2O5-MgO-SiO2 system was produced in our laboratory and used as the bioactive ceramic filler.