In this work an attempt has been made to determine the interaction mechanism between sodium tetradecyl sulfate (STS) and poly(vinylpyrrolidone) (PVP). The binding of ionic surfactant to PVP is discussed, and results of surfactant electrode and pyrene fluorescence measurements are reported. The slow relaxation times of STS were determined in the presence of different concentrations of PVP at various temperatures. Data were gathered from equilibrium and kinetic experiments, which together indicated the mechanism of the STS/PVP interaction system.