In this study, we introduce an alternative route for the synthesis of bioactive borate-phosphate glasses. Glasses with nominal compositions of xNa(2)O center dot yB(2)O(3)center dot zP(2)O(5) (x = 1, 2; y = 1/2; z = 1/2, 3/2) were obtained via melt-quench technique from B-O-P bonded materials prepared by organic-mediated synthesis. Analytical studies indicated that these glasses display different structural, thermal and surface characteristics compared to the known borophosphate glasses resulting from the orientation effect of the organic ligand present in the starting materials. In vitro bioactivity tests showed instant formation of amorphous calcium phosphates as apatite precursors. The unique properties of these newly-designed bioactive glasses might be improved for in situ bone regeneration and defect repair applications in orthopedics and dentistry. (C) 2014 Elsevier B.V. All rights reserved.