This article presents a study of the interaction of octadecanethiol molecules (Cm) with nanoporous cluster-assembled gold films under a liquid environment based on a combined spectroscopic ellipsometry and X-ray photoelectron spectroscopy investigation. By comparing the optical response, following the deposition of C(18), of cluster-assembled films with varying degrees of porosity with that of flat surfaces and by resolving the corresponding features of the molecule-Au bond, we have been able to define the conditions that either favor molecular in-depth diffusion into the pores or promote the formation of a molecular self-assembled monolayer (SAM) restricted to the film surface. In the presence of abundant open pores, C(18) molecules strongly diffuse within the film interior and bind to the pore walls, whereas in the presence of porous films with less abundant open pores we have observed that the molecules tend to remain confined to the surface region, adopting a SAM-like configuration.