Recently, it has been shown that using a single-site catalytic system it is possible to tailor entanglement density in the amorphous region of a semi-crystalline polymer, such as polyethylene, with a molar mass greater than 1 million g/mol. The synthesized polymer can be processed in its solid-state, along uniaxial and biaxial directions. It also shows strong heating rate dependence on melting invoking kinetics in randomization of chains from crystal to amorphous phase. With the help of solid-state NMR the distinction between amorphous regions of the synthesized and commercially available ultra-high molar mass polyethylene is made. For example, the polymer synthesized under the controlled conditions, using a homogeneous single-site catalytic system, shows faster motion of methylene units from the noncrystalline to the crystalline regions compared to commercially available nascent polyethylene synthesized using a Ziegler-Natta (Z-N) catalyst. The differences in chain diffusion, and the resultant 13C polarization transfer from the noncrystalline to the crystalline region, are attributed to the difference in entanglement density arising from the polymerization method employed. The two polyethylene samples investigated are of similar molar mass and crystallinity. Conformational changes caused by deformation of the two samples have been characterized and co-relationship with the entanglement density has been established. © 2012 Elsevier Ltd. All rights reserved.