The photocrosslinking of thick samples of 5‐ethylidene‐2‐norbornene–ethylene propylene diene monomer (ENB‐EPDM) under air at room temperature was investigated. First, a model study was carried out on low‐molecular weight oligomers: squalene, 1,2‐polybutadiene, and 1,4‐polybutadiene. Several crosslinking agents (meth(acrylics), bismaleimide, and thiol) combined with various photoinitiators were tested to improve the reactivity of these oligomers under UV irradiation. Gel contents, crosslinking densities, viscosities, and viscoelastic properties were measured in order to characterize the extent of crosslinking. Acrylate‐based crosslinking agents appeared to be the most reactive species and these results were then applied to a low‐molecular weight EPDM. Several photoinitiators were tested and benzophenone turned out to be the most efficient photoinitiator when combined with trimethylolpropane triacrylate. Finally, a commercial EPDM was subsequently photocrosslinked and high gel content and crosslinking density were obtained after only 2 min of irradiation. POLYM. ENG. SCI., 60:95–103, 2020. © 2019 Society of Plastics Engineers