Poly(ethylene oxide) (PEO) of molecular weight from 200,000 to 2,000,000 was crosslinked by exposure to ultraviolet radiation with a high-pressure 150 W mercury lamp. Photochemical crosslinking of PEO proceeds in the presence of photoinitiators such as benzophenone and acetophenone which act as a hydrogen-abstracting agent. Gel fraction yield exceeds 90%, and the number-average molecular weight between crosslinks determined by equilibrium swelling in chloroform varies from 3,000 to 100,000. The degree of crosslinking can be controlled by changing the irradiation temperature.