Membranes prepared for guided bone regeneration (GBR) signify valued resources, inhibiting fibrosis and assisting bone regenration. However, existing membranes lack bone regenerative capacity or adequate degradation profile. An alginate-casted polycaprolactone-gelatin-β-tricalcium phosphate dual membrane was fabricated by electrospinning and casting processes to enhance new bone formation under a GBR process. Porous membranes were synthesized with suitable hydrophilicity, swelling, and degradation behavior to confirm the compatibility of the product in the body. Furthermore, osteoblast-type cell toxicity and cell adhesion results showed that the electrospun membrane offered compatible environment to cells while the alginate sheet was found capable enough to supress the cellular attachment, but was a non-toxic material. Post-implantation, thein-vivooutcomes of the dual-layered membrane, showed appreciable bone formation. Significantly, osteoid islands had fused in the membrane group by eight weeks. The infiltration of fibrous tissues was blocked by the alginate membrane, and the ingrowth of new bone was enhanced. Immunocytochemical analysis indicated that the dual membrane could direct more proteins which control mineralization and convene osteoconductive properties of tissue-engineered bone grafts.