Molecular dynamics simulations were used to study the interfacial formation between pure and saline aqueous slabs and hydrophobic polytetrafluoroethylene (PTFE) surfaces, both porous and nonporous. The simulations revealed that the formation of transient water vapor bridges between the slabs and the hydrophobic surface facilitated initial contact by lowering the energy barrier, ultimately leading to surface adherence. The presence of saline aqueous slabs slowed the contact process and influenced the dynamics of the vapor-phase bridges. Additionally, porous PTFE surfaces accelerated the initial contact of the aqueous slabs and exhibited distinctive ion concentration gradients, particularly at the pore centers, indicating localized salinity. Structural deformations, such as bending and pore contact angles, were quantified, providing new insights into the nano-structural changes during the interactions between the slabs and PTFE surfaces.