Initiated chemical vapor deposition (iCVD) represents a novel CVD method for synthesizing polymer thin films in a single-step bottom-up polymerization-co-deposition process. Specifically, iCVD has been utilized to create poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels. FTIR and NMR evidenced the stoichiometric composition of PHEMA with full retention of chemical functionality. By controlling iCVD reaction kinetics, PHEMA deposition rate and molecular weight were successfully tuned, achieving rates as high as 1.5 μm/min, yielding high molecular weight polymers as observed through DSC. Because PHEMA hydrogels are polymers capable of absorbing substantial amounts of water and other liquid media, iCVD PHEMA has been studied and is demonstrated as a potential biomaterial to support living cell growth and as a potential polymer electrolyte material for dye sensitized solar cells.