Different alkylaluminums (triethyl-, tri-iso-butyl-, n-trihexylaluminum) were tested as activator for the iron complex LFeCl2 (1) (L=2,6-bis[(2,4,6-trimethylphenylimino)ethyl]pyridine) in ethylene polymerization. Various polymerization temperatures and the molar ratios of Al/Fe prepared polyethylene (PE) with different molecular weights, molecular weight distributions, polymerization activities and polyethylene structures. Through the analysis of in situ UV-vis absorption spectra, ethylene polymerization results and prepared polyethylene structures, the distinctive behaviors of the catalytic system could result from a new applicable mechanism involving two different kinds of catalytic species LFeRCl (a) and LFeR2 (b) (R = Et, i-Bu or He), the ratio of which varied with changing Al/Fe mole ratio when alkylaluminums were used as activators. The catalytic species (a) with very high activity mainly produced linear PE with high molecular weight in the bimodal PE. The catalytic species (b) with low activity mainly produced branched PE of low molecular weight in the bimodal PE. (c) 2005 Elsevier B.V. All rights reserved.