The hydrophobicity of a particle surface can be tuned by the addition of surfactants that change the surface free energy for their attachment to a liquid interface. In this work, we report an experimental study where the wettability properties of silica nanoparticles are modified by the adsorption of alkyltrimethylammonium surfactants (CnTAB, n = 12, 16) on the surface of the particles. We have pointed out that the wettability of the complexes is controlled by an intricate balance of electrostatic and hydrophobic interactions between the particle surface and the surfactant. These interactions play an important role in the structure of the surfactant–particle nanocomposite interfacial layer.