Molecular　level-based　silicate　bioactive　glass　(BG)-polymer　hybrid　materials　have　attracted　much　attention　in　bone　tissue　regeneration,　due　to　their　biomimetic　structure　and　bioactivity.　However,　few　successes　have　been　achieved　for　preparing　synthetic　biopolymers-based　bioactive　glass　hybrid　materials,　because　of　their　non-miscible　characteristic.　Here,　the　molecular　level　scale　bioactive　glass-poly　(epsilon-caprolactone)　(MBG-PCL)　hybrid　monoliths　with　porous　surface　structure　were　successfully　fabricated　by　a　polydimethylsiloxane　modified　sol-gel　technique.　The　as-prepared　hybrid　monolith　presented　a　porous　structure　and　crack-free　morphology.　The　in　vitro　bioactivity　test　showed　that　the　novel　MBG-PCL　hybrid　structure　exhibited　high　apatite-forming　ability　in　simulated　body　fluid　(SBF).　The　composition,　porous　structure,　as　well　as　high　bioactivity　of　the　hybrid　monoliths　make　them　a　promising　candidate　as　bioactive　implants　for　bone　tissue　regeneration.　(C)　2014　Elsevier　Ltd　and　Techna　Group　S.r.l.　All　rights　reserved.