The adsorption process of sodium dodecyl sulfate (SDS) at a hydrophobic layer was investigated by dual polarization interferometry (DPI), which provided the real-time information at solid/liquid interface. In dilute solution, the molecules adsorb at the surface as isotropic layer. With the increase in concentration, the molecules aggregate to form hemimicelles and the critical hemimicelles concentration (HMC) is 1 mM. The adsorption of SDS at C18 surface obeys two-step process. The competitive formations of micelles in solution and hemimicelles on C18 surface lead to particular adsorption behavior in higher concentration. We also proposed a four-stage adsorption model of SDS at C18 surface according to bulk concentration. (C) 2013 Elsevier Inc. All rights reserved.