The importance of polymeric transportation systems has been steadily increasing over the years. It is a useful material in numerous applications, such as packaging, oil and gas pipes, and household items. One particular aspect of polyethylene (PE) is the permeability of small molecules, such as low-molecular-weight hydrocarbons. In the present study, PE sheets were crosslinked by grafting and subsequent hydrolysis of organosilanes during a reactive extrusion process. The formation of a network structure was characterized by sol/gel analysis and by rheological measurements. It is shown that as a result of crosslinking the permeation of linear alkanes through the PE is reduced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45374.