We report the fabrication of a novel bilayer scaffold as a barrier membrane via modified-solvent casting and evaporation technique for the regeneration of bone defects. The blended solution of polycaprolactone (PCL) and calcium carbonate (CaCO3) was treated with hydrochloric acid (HCL), which resulted in the in situ formation of carbon dioxide (CO2) and water. This led to the phase separation between the PCL and calcium-based compounds and subsequently to the formation of a bilayer membrane. Surface morphology, surface wettability, and energy-dispersive X-ray spectroscopy (EDX) analysis confirmed the formation of a bilayered construct with a PCL-rich thin layer on the upper surface and a calcium-rich porous layer on the lower surface. From the FE-SEM images, the PC30 membrane showed a smooth upper layer with pores less than 10µm diameter, whereas the lower layer contained many interconnected larger pores up to 1000µm diameter in addition to the visibly identified macrovoids. The cell adhesion assay showed that both surfaces of the membrane responded well to the cells. In addition, the upper surface prevented the down-growth of the fibroblasts. The initial results suggest a new strategy for the fabrication of the bilayer membrane for regenerative medicine.