Measurements on paint components have been conducted with symmetrical flow field-flow fractionation (sym flow FFF) and asymmetrical flow FFF (asym flow FFF). Both methods are based on the same principle of separation, but they differ in the construction of the fractionation channel and the configuration of the channel flow and crossflow. On the basis of the good selectivity and resolution of these techniques, it was possible to determine the particle size of each individual constituent of a three-component mixture of a paint binder, pigment and filler, characterized by relatively broad and overlapping distributions, and to follow the changes on mixing them. In the case of sym flow FFF, it was possible to use thinner fractionation channels, with no system peaks and good selectivity in both the normal and steric-hyperlayer mode. The main features of asym flow FFF are the simpler construction of the fractionation channel and the possibility of focusing the sample in the channel better and of following visually the separation. This variant should be preferably used in the normal mode of operation.