Initiated Chemical Vapor Deposition (iCVD) is a solvent-free method that integrates polymerization and polymer processing into a single step to produce polymer thin films that are uniform and defect-free in benign synthesis conditions that retain functional moieties. Recently, the use of vapor solvents during iCVD has emerged as a promising strategy to enhance deposition rates and control film properties. This work aims to expand the understanding of iCVD films influenced by vapor solvents, with a focus on poly(acrylic acid) (PAA) thin films fabricated using triethylamine (TEA) as the vapor solvent. The research investigates the effects of vapor solvent inclusion on thermal, chemical, and physical properties, including glass transition temperature (Tg), polymer composition, and molecular weight. Key findings include the incorporation of TEA vapor solvent in the polymer films post-deposition and that vapor solvent can be removed from the film by heating above its boiling point, mitigating concerns about vapor solvent retention during applications. Other findings include depressed Tg values and increased molecular weight for vapor-solvent-assisted PAA films. These results provide critical insights into the use of vapor solvents in iCVD, highlighting benefits such as increased deposition rates, higher molecular weights, and the non-intrusive nature of vapor solvents upon removal.