Micro-thermal field-flow fractionation (mu-TFFF) was applied to the separation of polystyrene latices. This new high-resolution technique allows determination of the particle size distribution (PSD) if carried out under optimized experimental conditions. The optimum temperature of the accumulation wall, which influences the relaxation processes and, consequently, the zone broadening, was chosen on the basis of our prior work. The flow rate was chosen as a compromise between the theoretical optimum value, which is very low because the diffusion coefficients of the colloidal particles are very small, and a value allowing performance of the PSD analysis in a reasonable time. These experimental conditions can be manipulated easily due to the high versatility of mu-TFFF, which follows from a large decrease of the heat energy flux across the channel with its reduced dimensions in comparison with standard TFFF. The PSDs obtained from mu-TFFF data are compared with results from quasi-elastic laser light scattering (QELS) and transmission electron microscopy (TEM). It has been found that a baseline resolution of a model mixture of two samples of close average particle diameters can be achieved by an appropriate choice of the temperature drop in mu-TFFF, whereas only a broad, unresolved PSD of the mixed sample was obtained from the QELS measurement. The TEM of the mixed sample revealed the presence of two particle size populations. However, the number of particles which are practically counted on a TEM picture is several orders of magnitude lower than the number of particles taken into account in mu-TFFF or QELS. Consequently, the PSD obtained from the TEM did not represent the whole sample. Comparison of mu-TFFF with modern hydrodynamic chromatography (HC) has shown that the methods exhibit roughly the same resolution and time of analysis. Nevertheless, mu-TFFF is a more universal technique because the separation of the colloidal particles or of the macromolecules within a broad range of molar masses is carried out on the same channel, as demonstrated previously. (C) 2003 Elsevier Science (USA). All rights reserved.