Electrochemical methods can detect trace amounts of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the environment to help their management. PFAS adsorption on electrodes is an essential step in these methods, but is poorly understood. Here, we study the adsorption of perfluorooctanoic acid (PFOA), a model PFAS molecule, on gold substrates using metadynamics and equilibrium molecular dynamics simulations. The two-dimensional free energy landscape obtained from metadynamics reveals that a PFOA molecule can adsorb on a neutral gold surface with the lowest free energy of −83.9 kJ/mol by adopting a co-planar orientation, indicating a strong enrichment of PFOA occurs near the electrode. Spontaneous adsorption in other configurations, e. g., only a PFOA molecule‘s head attaches to the electrode, also occurs. However, a PFOA molecule generally must overcome energy barriers to become adsorbed. We show that energetic effects, particularly those associated with van der Waals PFOA-gold interactions, are the primary driver for PFOA adsorption, and entropic effects associated with interfacial water molecules are the secondary driver. The implications of these results for the electrochemical detection and analysis of PFAS molecules are discussed.