Perfluorooctanoic acid (PFOA) is an important perfluorinated chemical of significant environmental concern. It has been widely found at high concentrations in the environment. We have exposed sediment constituent minerals SiO2, Fe2O3, and Al2O3 to PFOA and humic acid (HA) and studied the adsorption of PFOA by introducing the adsorbates in different orders. The results suggest concurrent sorption of PFOA and HA to the mineral surface or enhanced PFOA sorption when both are introduced to the aqueous phase. However, when PFOA is introduced to the mineral surface that has already been exposed to and extensively coated with HA, little PFOA adsorption occurs, which implies that PFOA released to rivers rich in dissolved organic matter (DOM, i.e. HA) may be immune to sorptive retention by the sediment and be transported downstream unabated. DOM thus can play a significant role in the transport and fate of PFOA in the natural water system.