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This work deals with the application of the static light scattering (SLS) model of Vrij (VM) for the characterization of a spherical polydisperse concentrated polymer particle system. This model is the exact solution for the SLS of such mixture of particles in the Percus–Yevick approximation. The analyzed polymer particle samples are obtained by solution polymerization of isobornyl methacrylate in polyisobutylene. At the end of the polymerization, as a result of phase separation, a particle system of micrometer sized particles with a moderate distribution of sizes and a volume fraction between 5 and 10% is formed. The SLS data were also analyzed using the local monodisperse approximation (LMA), a well‐known approximation to the model of Vrij. As expected, the estimations with the VM gave better results than those performed with the LMA model for the parameters related to the shape of the particle size distribution as compared with independent determinations of these quantities obtained from scanning electron microscopy micrographs. However, the main motivation to use the more rigorous model seems to be the fact that the volume fraction of particles can be extracted from the data even when relative SLS measurements are used. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 958–963, 2010