The limitations associated with the clinical use of autographs and allografts are driving efforts to develop relevant and applicable biomaterial substitutes. In this research, 3D porous scaffolds composed of bioactive glass (BG) obtained through the sol-gel technique and polylactic acid (PLA) synthesized via lactic acid (LA) ring-opening polymerization were prepared by the gel-pressing technique. Two different weight compositions were evaluated, namely, BG70-PLA30 and BG30-PLA70. The structure and morphology of the resulting scaffolds were analysed by FTIR, XRD, SEM, and under ASTM F1635 standard characterizations. The results confirmed that BG promotes the formation of a hydroxy-carbonated apatite (HAp) layer on composites when immersed in simulated body fluid (SBF). Biodegradability evaluations were carried out according to the ISO 10993-13:2010 standard. In addition, electrochemical evaluations were performed in both Hank’s and SBF solutions at 37 °C in order to analyse the degradation of the material. This evaluation allowed us to observe that both samples showed an activation mechanism in the early stages followed by pseudo-passivation due to physical bioactive glass characteristics, suggesting an improvement in the formation of the HAp nucleation. The described composites showed excellent resistance to degradation and outstanding suitability for bone tissue engineering applications.