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