PHBV ultrafine fibers were fabricated by electrospinning process. Electrospun PHBV fiber structures revealed randomly aligned fibers with average diameter of 400 nm. PIPAAm was grafted on the surface of PHBV nanofibrous mat by electron beam irradiation. PIPAAm-grafted PHBV mats were determined by ATR-FTIR and ESCA. Water contact angles were determined by a sessile drop method at 20 and 37. To examine the tissue compatibility, human fibroblasts were evenly seeded onto PIPAAm-grafted PHBV mat and cast film, ungrafted PHBV mat and film. Attached and spread fibroblasts on nanofibrous mat were proliferated more rapidly than that of flat film surface. Initial cell attachment on PIPAAm-grafted surfaces was higher than ungrafted surfaces. The surface property changed to hydrophilic by PIPAAm graft, which increased initial cell attachment. Detachment of single cells from PIPAAm-grafted PHBV matrixes was measured by low temperature treatment after incubation at 37. Cultured cells were rapidly detached from PIPAAm-grafted PHBV mat compared with film. With porous mats, the water molecules easily reach to grafted PIPAAm from underneath and peripheral to the attached cells, resulting in rapid hydration of grafted PIPAAm molecules and detachment of the cells.