This paper focuses on an effective way to improve the thermostability of poly-β-hydroxybutyrate (PHB). Maleic anhydride (MA) is grafted onto PHB by 60Co γ of radiation. The spectra of both 1HNMR and 13CNMR were investigated following the radiation-induced polymerization. The results are consistent with successful grafting of the MA monomer onto the PHB, with a low graft degree. The graft degree and viscosity-average molecular weight Mηof the radiated samples were also investigated. The results observed through TGA demonstrate that thermostability has been measurably improved with the introduction of MA groups. These significant results suggest that wide commercial application of PHB may be possible.