To reveal and control the differentiation and proliferation of the periodontal ligament (PDL) cells and to develop a highly organized hybrid implant possessing periodontium, hydroxyapatite (HAP) was immobilized on the poly(ethylene-co-vinyl alcohol) (EVA) by alternate soaking method following with carboxyl groups' introduction through ozone exposure. Human PDL cells were cultured on the ozone-exposed EVA, collagen-immobilized EVA, HAP-immobilized EVA, HAP plate, tricalcium phosphate plate, and conventional tissue culture dish. Cell proliferation was highest on the collagen-immobilized EVA and lowest on the HAP-immobilized EVA. Alkaline phosphatase activity and osteocalcin secretion were highest on the HAP-immobilized EVA. These results suggest that PDL cells were differentiated toward bone-like cells on the HAP-immobilized EVA.