The coupling reaction of melt linear low density polyethylene (LLDPE) initiated by dicurnyl peroxide (DCP) in steady shear flow field was investigated. The conversion of DCP was measured by electron spin resonance (ESR) and chemical titration. An absolute method was proposed to calculate the actual conversion of DCP from rheological data. The coupling efficiency of DCP was obtained from those analyses, which was shown to increase at first, reach a maximum and then decrease in the end stage. A linear relationship between the coupling efficiency of DCP and the concentration of macroradicals was also found in the experiments. (c) 2005 Elsevier Ltd. All rights reserved.