Thermal field‐flow fractionation (ThFFF) is a powerful method for analytical and semi‐preparative particle separations according to colloidal properties. State of the art in terms of experiment and theory are reviewed. Surfactant‐free ThFFF is introduced, allowing for determination of method‐independent Soret coefficients, whereas significant electrostatic and van der Waals interactions in the channel have to be accounted. In these conditions, superior sensitivity of ThFFF on particle surface properties is demonstrated, as well as crucial dependence of fractionation of the ionic strength of the carrier. Electrostatic submechanisms to thermophoresis of charged colloids are discussed. Specific salt‐dependent fractionation is investigated in solutions mixed from NaCl and NaOH. Simulations are in good agreement with experimental data, and observed sign inversion of thermophoresis is shown to arise from thermoelectric effects. Also, temperature dependence of model colloids is simulated to be governed by electrostatic forces.