In this article, the effect of diethylaluminum chloride (DEAC) in propylene polymerization with MgCl2-supported Ziegler-Natta catalyst was studied. Addition of DEAC in the catalyst system caused evident change in catalytic activity and polymer chain structure. The activity decrease in raising DEAC/Ti molar ratio from 0 to 2 is a result of depressed production of isotactic polypropylene chains. The number of active centers in fractions of each polymer sample was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and fractionating the polymer into isotactic, medium-isotactic and atactic fractions. The number of active centers in isotactic fraction ([Ci*]/[Ti]) was lowered by increasing DEAC/Ti molar ratio to 2, but further increasing the DEAC/Ti molar ratio to 20 caused marked increase of [Ci*]/[Ti]. The number of active centers that produce atactic and medium-isotactic PP chains was less influenced by DEAC in the range of DEAC/Ti = 0-10, but increased when the DEAC/Ti molar ratio was further raised to 20. The propagation rate constant of Ci * (kpi) was evidently increased when DEAC/Ti molar ratio was raised from 0 to 5, but further increase in DEAC/Ti ratio caused gradual decrease in k pi . The complicated effect of DEAC on the polymerization kinetics, catalysis behaviors and polymer structure can be reasonably explained by adsorption of DEAC on the central metal of the active centers or on Mg atoms adjacent to the central metal. In this article, the effect of diethylaluminum chloride (DEAC) in propylene polymerization with MgCl2-supported Ziegler-Natta catalyst was studied. Addition of DEAC in the catalyst system caused evident change in catalytic activity and polymer chain structure. The activity decrease in raising DEAC The number of active centers in fractions of each polymer sample was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and fractionating the polymer into isotactic, medium- The number of active centers in isotactic fraction ([Ci *] / [Ti]) was lowered by increasing DEAC / Ti molar ratio to 2, but further increasing the DEAC / Ti molar ratio to 20 caused marked increase of [Number of active centers that produce atactic and medium-isotactic PP chains was less influenced by DEAC in the range of DEAC / Ti = 0-10, but increased when the The DEAC / Ti molar ratio was further raised to 20. The propagation rate constant of Ci * (kpi) was evidently increased when the DEAC / Ti molar ratio was raised from 0 to 5, but further increase in DEAC / Ti ratio caused gradual decrease in k pi. The complicated effect of DEAC on the polymerization kinetics, catalysis behaviors and polymer structure can be reasonably explained by adsorption of DEAC on the central metal of the active centers or on Mg atoms adjacent to the central metal.