AbstractPhotografting polymerization of polyacrylamide (PAM) onto poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) films using benzophenone as photoinitiator was studied. The morphology and structure of the grafted PHBV film were characterized by Fourier transformed infrared spectroscopy (FTIR) with attenuated total reflectance (ATR) and scanning electron microscope (SEM) with energy dispersive X‐ray spectrometer (EDX). The grafting percentage and grafting efficiency of the grafted PHBV film went up with the increase of acrylamide concentration and irradiation time. It was observed that photografting polymerization of PAM was not only limited to the film surface, but also in situ occurred inside the film to form the pore microstructure. Sheep bone marrow stromal cell studies showed that MSCs cells attachment efficiency on the grafted PHBV films increased and cells grew well. These results demonstrated the potentiality of PAM‐photografting PHBV in medical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4088–4095, 2007