Abstract E.s.r. spectra of chain-end spin labels on the surface of polyethylene powder were obtained for high and low density polyethylene samples at various stages of heat treatment process. The subsequent crystalline structures of the samples were examined with wide angle and small angle X-ray diffraction spectra. The effects of annealing on the motion of the labels were dependent on annealing temperature and the type of the samples. Higher temperature annealing decreased the rotational correlation times ( τ c ) and their activation energy in high density polyethylene but did not affect those of low density polyethylene. Melting decreases the values of τ c and ΔE for both high an low density polyethylene samples. The cause of these decreases were attributed to the changing of the sites of the chain-end labels. The motion of the labels appeared to be influenced by the local segmental motion of the polymer main chains.