Abstract: The charge equilibration (QEq) method was adopted to calculate the charge distribution along the linear polyethylene (PE) chains. It was found that the CH3 and CH2 groups in the non-polar PE chain have non-zero charges. Then the single PE chain was found to be able to reorient in the high electric field by the MD simulation. At last, the QEq method was applied in calculating the charge distribution in the multi-chain PE systems both in vacuum and in bulk condition, and the MD simulation revealed that the PE systems in both conditions can be reoriented. The original reason for this reorientation phenomenon was the asymmetry of the charge distribution along the chains.