Low-density polyethylene (LDPE) has been functionalized in the bulk through dicumyl peroxide (DCP)-initiated grafting of dibutyl maleate (DBM) and vinyltrimethoxysilane (VTMO) in the temperature range from 140 to 200°C. The functionalized surfaces have been characterized through contact angle and contact-angle hysteresis measurements as well as through ESCA studies. The degree of grafting has been determined by infrared spectrophotometry. From the ESCA patterns of the modified polymers, the atomic ratios of oxygen to carbon and silicon to carbon have been calculated. Determination of an empirical relation between contact-angle hysteresis and the oxygen-carbon ratio of the functionalized polymer surfaces has been attempted. It is found that the higher the oxygen-carbon ratio, the lower the contact-angle value for polyethylene. Contact angle-hysteresis increases with increase of the degree of grafting. The total surface energy increases with grafting. The surface energy of the silane-grafted polyethylene (PEgS) is found to be the lower than that of dibutyl maleate-grafted polyethylene (PEgDBM). © 1993 John Wiley & Sons, Inc.