Surface elemental compositions of model latex clay coatings on an impervious substrate consolidated under various conditions were measured using the XPS technique, in order to clarify when and how colloidal latex particles migrate to the surface during drying. Under similar drying conditions, surface carbon content decreased with the addition of a water-soluble polymer to the coating colors, while remaining virtually unchanged for coatings of different coat weights made with a given color, indicating that surface carbon content variation is mainly caused by migration of latex rather than of water-soluble polymer. The results also showed that for coatings made with a given suspension, surface carbon content decreased with increasing delay time between coating and heating. For coatings frozen during consolidation and dried by sublimation, surface carbon content increased with increasing drying time before freezing. These results suggest that for the model coatings studied, latex migration mainly occurs after coating application before capillary formation during the initial drying stage when coatings are in the liquid phase, contradicting both the conventional capillary transport and boundary wall migration mechanisms. An alternative mechanism which attributes latex migration to surface trapping effect and to higher Brownian mobility of the smaller latex particles compared with pigment appears to provide a systematically consistent explanation to those phenomena. The new particle migration mechanism implies that segregation of colloidal particles is a ubiquitous phenomenon that would occur not only during the drying of paper coatings but also during consolidation of colloidal films containing particles of different sizes. This is of great importance in the control of surface compositions of nanocomposite coatings.