A novel poly(lactic acid) (PLA)/calcium carbonates hybrid membrane containing silica was prepared using aminopropyltriethoxysilane (APTES) for biodegradable bone guided regeneration. Carboxy groups in PLA made a chemical bond with amino groups in APTES, resulting in the formation of the hybrid membrane. The silica-hybridized PLA was an amorphous phase. The membrane formed hydroxycarbonate apatite (HCA) on its surface after 3 d of soaking in simulated body fluid (SBF). After soaking the membrane in SBF, almost no Si was present in SBF. X-ray energy dispersive spectroscopy showed the HCA layer includes Si with Ca and P. A result of osteoblast-like cellular proliferation on the membrane showed no cell-toxicity.