This study demonstrates the coating of a transparent and robust organic thin film having an excellent hydrophilicity-based antifogging property by an initiated chemical vapor deposition (iCVD) method. iCVD was able to synthesize linear and cross-liked poly(acrylic acid) (PAA) from the vapors of acrylic acid (AA) and ethylene glycol dimethacrylate (EGDMA) using tert-butyl peroxide (TBPO) as an initiator. High deposition rates of up to 35 nm/min were observed at low deposition temperatures. It was possible to control the quantity of comonomers in the as-deposited films by adjusting the partial pressure of the EGDMA cross-linking agent. The effect of the EGDMA partial pressure on chemical structure was studied using Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) techniques. FTIR and XPS spectra of the as-deposited films showed the complete retention of the monomer functionality during iCVD. Hydrophilicities and large-area uniformity of the coatings were revealed using water contact angle measurements. The as-deposited PAA film was the most hydrophilic with a water contact angle (WCA) of 7.0 degrees, while cross-linking with EGDMA increased the WCA values by up to 51.7 degrees. Results of various tests, which were based on exposing the coated surfaces to artificial fog and hot water vapor, showed the excellent antifogging property of the coatings. Films were never fogged upon extensive and long-term exposure (2 months) to humid air.