This study reports on the effects of electron beam radiation on pullulan in both the dry state and hydro-methanolic blends containing cinnamyl alcohol (CA). The radiation chemical yields of scission (G(S)) and crosslinking (G(X)) were determined using Saito’s formalism applied to the evolution of molecular weight (MW) with increasing absorbed dose of radiation. To satisfy the requirements of the statistical treatment, commercially available pullulan was fractionated to obtain a monomodal MW distribution with a dispersity close to 2. The changes in MW profiles were monitored by SEC with differential refractive index and UV detection. The introduction of small quantities of CA in the pullulan blends led to a significant decrease in G(S) and G(X), protecting pullulan against radiation-induced effects likely via energy and electron transfer. In presence of larger amounts of CA, irradiation at higher dose induced an increase in molecular mass with concomitant grafting of the aromatic additive.