Structures of cross-links produced in benzophenone-photoinitiated cross-linking of low-density polyethylene (LDPE) and a model compound n-C24H50 have been studied for the first time by solution-state C-13 NMR spectroscopy. Well-resolved resonance lines, assigned to CHH, alpha-CH2, and beta-CH2 groups related to H-cross-links, have been observed for the photo-cross-linked samples below the gel dose. At the same time, the resonance lines associated with Y-type long branches are also found to be significantly formed during the photoinitiated cross-linking of LDPE. The concentrations of H-links and Y-branches are estimated to be 5.7-16.9 and 7.6-21.6 per 10 000 carbon atoms, respectively, for the samples UV-irradiated for 5-10 s in the melt, indicating that Y-links also are effectively produced in the photoinitiated LDPE samples. These results are slightly but significantly different from those reported for high-energy radiation-induced cross-linking of high-density polyethylene.