Biosynthetic poly[(R)-3-hydroxybutyrate] (PHB) undergoes a deleterious ageing process which has been attributed to progressive crystallisation. In this work an attempt has been made to arrest this crystallisation behaviour by an irradiation treatment which is known to induce cross-linking in many polymers. PHB films were irradiated with different doses of electrons and at different times after the initiation of crystallisation. The degree of crystallinity was subsequently determined as a function of time after irradiation using wide-angle X-ray scattering measurements. In addition, melting endotherms were obtained by differential scanning calorimetry (DSC) and molecular weights by gel permeation chromatography (GPC). Corresponding tensile stress-strain experiments were performed in order to obtain information on the mechanical properties of the sample films. The melting point and molecular weights were found to decrease linearly with radiation dose indicating that higher radiation doses cause degradation due to chain scission. However, lower doses applied to samples still in their amorphous state indicate a high degree of cross-linking, in which a network is formed and the ageing process can be prevented to some extent. The tensile modulus and breaking strain were influenced strongly by the point in time at which the material was irradiated during crystallisation.