The wetting behaviors of thin polymer films are known to be unique in comparison to bulk material and influenced by interfacial effects in an unknown, complex manner. Our approach to studying intermolecular interactions and their effects on wetting involves the investigation of contact angle measurements on multilayered, ultrathin polymer films and their dependence on film thickness. A large critical thickness (~100 nm) for the dependence of water contact angle measurements on polystyrene (PS) films is observed across literature. This highlights a gap in the current understanding of wetting in the ultrathin length scale, where the additive contributions from long-range vdW forces cannot fully explain the observed thickness dependence of contact angle measurements. Two crosslinked polymer bilayer systems of PS and poly(methyl methacrylate) (PMMA) are used to deconvolute wetting contributions from changes in material properties due to geometric confinement and interfacial effects due to additive, long-range van der Waals forces. Additionally, several challenges to fabricating ultrathin polymer film samples for contact angle measurements are identified. Initiated chemical vapor deposition (iCVD) is explored as a technique to fabricate large-scale, uniform polymer films of sub-10 nm thickness advantageous for wettability studies. It is determined that deposited film topography depends on iCVD conditions and the wetting favorability of the substrate. The concentration of monomer at the substrate surface (Pm/Psat) is shown to be a key variable to dictate the resulting film topography. In turn, contact angles on the films are shown to depend on iCVD conditions. This is highlighted by the development of a data management system for uniform analysis of advancing/receding contact angle (ACA/RCA) measurements, which uncovered correlations between the contact angle measurements. The need for uniform analysis of ACA/RCA is discussed, which motivates the development of an automated method to uniformly process data by a mathematical definition. This method is used to process all ACA/RCA measurements. In addition, a novel method to investigate the wettability of reactive interfaces in real-time is developed. Multiple representations of wettability as surface functionalization are achieved within a singular experiment. Overall, these findings contribute to a further understanding of the unique wetting behaviors of thin polymer films and guide future investigation of wetting via contact angle measurements.