The supermolecular structure of photocross-linked polyethylene (XLPE) has been studied by small-angle light scattering (SALS). The data show that the spherulitic structure of XLPE gradually deteriorates with increasing degree of cross-linking and increasing irradiation temperature from well-developed spherulites to rodlike aggregates and disordered lamellar structures. A photocross-linked sample of PE has lower crystallinity, smaller crystallites, and smaller spherulites than does the original sample. At high degrees of cross-linking, the SALS patterns show little or no spherulitic structure. Results with photocross-linked polyethylene demonstrate that the overall effect of cross-linking on the morphological structure is similar to that of an increase in molecular weight of the polymer. © 1993 John Wiley & Sons, Inc.