Mesoporous silicate glass (MSG) doped with biomaterials has gained significant attention for enhancing bone tissue regeneration, particularly through promoting hydroxyl-carbonate-apatite (HCA) formation. However, the use of boron in MSG is constrained by the structural instability of boron-modified matrices. In this work, phosphorus-doped boron-containing mesoporous silicate glass scaffolds (BMSGS) based on PCL/PLA were made using a solvent casting-assisted particulate leaching technique. The effect of phosphorus doping on scaffold morphology and bioactivity was assessed using various analytical techniques including XRD, FESEM, nitrogen physisorption isotherms, and FTIR spectroscopy. Increasing phosphorus doping beyond 10 mol% induced significant structural reorganization with the BET surface area increasing from 130 m2g-1 to 306 m2g-1 and optimal performance of 278 m2g-1 surface area (SBP10 sample). The SBP-PPS10 scaffold sample exhibited superior porosity of 63.4 %, faster biodegradation, and accelerated HCA formation, and improved bioactivity. These findings revealed a novel strategy for improving the bioactivity and stability of boron-doped MSG through phosphorus incorporation, offering new insights into the design of advanced materials for bone regeneration applications. © 2025 Elsevier Ltd and Techna Group S.r.l.