AbstractCold plasma treatment in the melt state is a novel area of research focused on producing modified polymers, hence more research on the underlying plasma‐polymer interactions in this context is needed. In this study, low‐density polyethylene (LDPE) was treated with a cold atmospheric pressure plasma jet (CAPPJ) during melt processing in a polymer batch mixer. Electron spin resonance (ESR) results proved that plasma treatment effectively generates free radicals in the material, increasing the room temperature spin concentration by an order of magnitude to 2 × 1015 spins g−1. The generated radicals react mainly by cross‐linking, forming a gel phase of up to 31%, and consequently increasing the polymer's melt viscosity. Furthermore, oxidation was established as solely a thermal effect limited by radical availability at the interface exposed to the atmosphere, whereas plasma exposure did not lead to further oxidation. Interestingly, plasma appears to interact with the thermally created ketone groups, possibly forming unsaturated carbonyl compounds.