The phenomenon of electrification is the accumulation of electric charge in a material. Polymers may become electrified when subjected to intense friction during their processing or under working conditions and the accumulated electric charge may change their adhesion and friction properties. In this work, a study of the influence of molecular weight and chain mobility on the electrification of linear low-density polyethylenes under continuous extrusion is presented. The use of different die materials, polymer processing additives, as well as slip and no slip flow conditions allowed the identification of two different mechanisms for electric charge generation in the melts; namely, the stripping of an electrical double layer acting in the absence of slip, and dynamic frictional electrification, or tribocharging acting under strong slip conditions. The magnitude of the electric charge was found to increase with polymer molecular weight and die length, and exhibited a local maximum as a function of the average velocity of the melt in both cases. The height of the maximum increased along with the molecular mobility. The experimental results were compared with the numerical solution of the equation of continuity for charge transport and it is shown that it does not describe the experimental results because it does not consider the additional mechanism of charge generation introduced by strong slip at the die wall. POLYM. ENG. SCI., 48:386-394,2008. (c) 2007 Society of Plastics Engineers.