To analyze the natural rubber behavior during vulcanization under different cure treatments, an experimental investigation using small angle X-ray scattering was performed. To achieve this, a set of samples were prepared using sulfur and N-t-butyl-2-benzothiazole sulfenamide as accelerator and then cured at temperatures between 403 and 463 K reaching their optimum mechanical properties considering rheometer tests. The crosslink density of the samples was evaluated by means of the swelling technique in solvent. In the usual Lorentz corrected representation of the X-ray scattered intensity, a maximum was observed in the plots corresponding to the cured samples, revealing a highly correlated structure. This maximum shifted toward higher values of the scattering vector when the cure temperature of the samples increased. This behavior is discussed in terms of the crosslinks type present in the vulcanized rubber network at different cure temperatures. (C) 2007 Wiley Periodicals, Inc.