A poly(styrene-co-hydroxyethylmethacrylate) latex underwent sedimentation under gravity followed by an spontaneous and extensive colloidal crystallization. It was then fractionated in three visually distinguishable layers. Latex aliquots layers were sampled at different heigths and the particles were characterized by PCS, microelectrophoresis, infrared spectra and analytical electron microscopy. The major fraction was opalescent and contained the colloidal crystals settled in the bottom of the liquid. Two other latex fractions were obtained, which differed in their chemical compositions, particle sizes and topochemical features from the self-arraying particles. Macrocrystallization of the fractionated latex yielded high quality crystals with a low frequency of defects, which confirms that particle chemical homogeneity is an important factor for particle self-arraying.