Composites based on natural rubber and plasticized starch obtained by the conventional method of sulfur cross-linking using four types of vulcanization accelerators (Diphenyl guanidine, 2-Mercaptobenzothiazole, N-Cyclohexyl-2-benzothiazole sulfenamide, and Tetramethylthiuram disulfide) were irradiated with an electron beam in the dose range of 150 and 450 kGy for the purpose of degradation. The vulcanization accelerators were used in different percentages and combinations, resulting in four mixtures with different potential during the cross-linking process (synergistic, activator, or additive). The resulting composites were investigated before and after irradiation in order to establish a connection between the type of accelerator mixture, irradiation dose, and composite properties (gel fraction, cross-linking degree, water absorption, mass loss in water and toluene, mechanical properties, and structural and morphological properties). The results showed that the mixtures became sensitive at the irradiation dose of 300 kGy and at the irradiation dose of 450 kGy, and the consequences of the degradation processes were discussed.