The effect of elevated temperatures (40, 80, and 170 °C) on the electron beam (EB)‐induced crosslinking and degradation of poly(ε‐caprolactone) (PCL) in nitrogen atmosphere without adding crosslinking agents has been investigated. The increased mass average molecular mass of EB modified masticated PCL (mPCL) samples were measured by size exclusion chromatography. The sol–gel investigation showed that mPCL tended to dominating crosslinking at a temperature of 170 °C. At this temperature, the maximum gel content of 56% was observed for an EB treatment with a dose of 100 kGy. In addition, the ratio of chain scission density to density of crosslinked units amounted to 0.25. The dynamic rheological test demonstrated that EB treatment at 170 °C led to the most remarkable elasticity enhancement behavior with enhanced viscosity, modulus, and decreased loss factor (tan δ). The occurrence of branching structure was evidently detected by van Gurp–Palmen plot in combination with the Cole–Cole plot for dose values ≤50 kGy. Less δ and a broadened relaxation process can be observed due to the introduction of some branched structures into mPCL. The results of enhanced molar mass and gel content analysis were confirmed by the dynamic rheological measurements. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47866.