Chemical vapor deposition of polymer films eliminates the need for organic solvents and thereby offers a safer and cleaner alternative to liquid‐phase processing. This article discusses the mechanism, benefits, and capabilities associated with several types of vapor‐phase polymerization methods with a particular emphasis on initiated chemical vapor deposition (iCVD) and oxidative chemical vapor deposition (oCVD). The iCVD technique can be used to produce films that exhibit a wide range of properties such as hydrophobicity, hydrophilicity, and responsiveness to heat, pH, and light, whereas the oCVD method can be used to make conductive films. These deposition techniques allow for the controlled fabrication of high molecular weight polymer films with deposition rates as fast as several hundred nanometers per minute and can be used to modify the surfaces of three‐dimensional curved, pillared, and porous substrates since there are no solvent tension effects such as clogging or wetting.