The effects of high energy ball milling (HEBM) on the structure and some key-properties of crosslinked high density polyethylene (PEX) have been thoroughly examined with a combination of X-ray diffraction analysis, IR and Raman spectroscopy, differential scanning calorimetry, gel content measurements, and tensile properties tests. A structure-property relationship, which provides a reasonable explanation for the studied case has been developed based on the experimental results and their analysis. It is proposed that the HEBM provides some of the silane-grafted macromolecular chains, which have a specific orientation, with sufficient energy in order to crosslink and form small crystalline-like areas. The arrangement of chains in the "reformed" domains leads to a total increase of the overall crystallinity, but also a decrease of the crystalline size. The proposed model can also support the fact that by increasing the milling time, the overall crystallinity of PEX and some important mechanical properties are found to increase.