The silane grafting and moisture crosslinking of different grades of polyethylene have been investigated. Three types of polyethylene (HDPE, LLDPE, and LDPE) with different molecular structures and similar melt flow indices were selected. The initiator was dicumyl peroxide (DCP), and the silane was vinyltrimethoxysilane. The grafting reaction was carried out in an internal mixer. The extent of grafting and the degree of crosslinking were determined, and hot-set tests were carried out to evaluate the crosslink structure of the different polyethylenes. The LLDPE had the highest degree of grafting, while the LDPE had the least. The rate of crosslinking for LDPE was higher than that of HDPE and LLDPE. The gel content of LDPE was higher than that of HDPE and LLDPE. Hot-set elongation and the number-average molecular weight between crosslinks (M c ) were lower for LLDPE and LDPE than for HDPE. Increasing the silane/DCP percentage led to peroxide crosslinking, thereby decreasing the M c and hot-set elongation. The number-average molecular weight (M n ), molecular weight distribution, and number of chain branches were the most important parameters affecting the silane grafting and moisture crosslinking.