Water, methanol (MeOH), acetonitrile (ACN), and binary MeOH-water and ACN-water solutions of different spin probes (nitroxides), selected to mimic the behavior of different pollutants, were adsorbed onto stationary phases usually used in reversed-phase high-performance liquid chromatography (RP-HPLC). These stationary phases are constituted by porous silica and differ from each other regarding the surface area, the pore size, the particle size, the surface functions (NH2, C8, and C18), and the percentage of functionalization. The electron paramagnetic resonance (EPR) spectra of the probe solutions adsorbed into the pores were analyzed by computer-aided computation of the spectral line shape, which provided structural and dynamical parameters of the probes and their environments. These parameters provided information on the surface properties of the stationary phases, such as alkyl chain density, solvent penetration, stationary-phase ordering, and residual silanol effects, which modify the retention times in HPLC. A different availability of polar surface groups in the pure and mixed solvents was found for the different stationary phases depending on (1) the different functionalization degree, (2) the surface-chain length, (3) the particle size, and (4) the polarity of both the probe and the solvent. The C8 functionalization rendered the surface more hydrophobic with respect to C18. The endcapping process of the residual silanols strongly enhanced the surface hydrophobicity tested by the probes. At the highest water content, the adsorption of the polar or charged probes onto the hydrophobic surface is the lowest and self-aggregation occurs. When the probes bear both hydrophilic and hydrophobic moieties, the adsorption is enhanced by a synergy between hydrophilic and hydrophobic bonds with the surface. A balance between the hydrophilic and hydrophobic forces leads to high adsorption and partial insertion of the surfactant probes in an ordered C18 chain layer at the solid surface which forms in the binary mixtures; this layer is ascertained between 40% and 70% of the less hydrophilic solvent, depending on the type of both the solid and the probe. This insertion and the response on the formation of the ordered layer were favored in ACN-water with respect to MeOH-water.